Iron(0) and ruthenium(0) complexes with tridentate phosphonite ligands and their potential for ketene formation from methyl iodide, CO and a base

Journal of Organometallic Chemistry 690 (2005) 1429–1455

www.elsevier.com/locate/jorganchem

Iron(0) and ruthenium(0) complexes with tridentate

phosphonite ligands and their potential for ketene formation

from methyl iodide, CO and a base

*

Piotr Jaunky, Helmut W. Schmalle, Olivier Blacque, Thomas Fox, Heinz Berke

Anorganisch-chemisches Institut, Universita¨t Zu¨rich, Winterthurerstrasse 190, CH-8057 Zu¨rich, Switzerland

Received 26 September 2004; accepted 18 November 2004

Available online 22 January 2005

Abstract

An eﬃcient route to the novel tridentate phosphine ligands RP[CH₂CH₂CH₂P(OR⁰)₂]₂(I: R = Ph; R⁰= i-Pr; II: R = Cy; R⁰=

i-Pr; III: R = Ph; R⁰= Me and IV: R = Cy; R⁰= Me) has been developed. The corresponding ruthenium and iron dicarbonyl com-

plexes M(triphos)(CO)₂(1: M = Ru; triphos = I; 2: M = Ru; triphos = II; 3: M = Ru; triphos = III; 4: M = Ru; triphos = IV; 5:

M = Fe; triphos = I; 6: M = Fe; triphos = II; 7: M = Fe; triphos = III and 8: M = Fe; triphos = IV) have been prepared and fully

characterized. The structures of 1, 3 and 5 have been established by X-ray diﬀraction studies. The oxidative addition of MeI to

1–8 produces a mixture of the corresponding isomeric octahedral cationic complexes mer,trans-(13a–20a) and mer,cis-[M(Me)(tri-

phos)(CO)₂]I (13b–20b) (M = Ru, Fe; triphos = I–IV). The structures of 13a and 20a (as the tetraphenylborate salt (21)) have been

veriﬁed by X-ray diﬀraction studies. The oxidative addition of other alkyl iodides (EtI, i-PrI and n-PrI) to 1–8 did not aﬀord the

corresponding alkyl metal complexes and rather the cationic octahedral iodo complexes mer,cis-[M(I)(triphos)(CO)₂]I (22–29)

(M = Ru, Fe; triphos = I–IV) were produced. Complexes 22–29 could also be obtained by the addition of a stoichiometric amount

of I₂to 1–8. The structure of 22 has been veriﬁed by an X-ray diﬀraction study. Reaction of 13a/b–20a/b with CO aﬀorded the acetyl

complexes mer,trans-[M(COMe)(triphos)(CO)₂]I, 30–37, respectively (M = Ru, Fe; triphos = I–IV). The ruthenium acetyl complexes

30–33 reacted slowly with 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) even in boiling

acetonitrile. Under the same conditions, the deprotonation reactions of the iron acetyl complexes 34–37 were completed within 24–

40 h to aﬀord the corresponding zero valent complexes 5–8. It was not possible to observe the intermediate ketene complexes. Trac-

ing of the released ketene was attempted by deprotonation studies on the labelled species mer,trans-[Fe(COCD₃)(triphos)(CO)₂]I

(38) and mer,trans-[Fe(¹³COMe)(triphos)(CO)₂]I (39).

Keywords: Iron; Ruthenium; Phosphonite; Oxidative addition; Ketene

1. Introduction

of the acyl complexes may aﬀord the corresponding ke-

tene complexes. Ultimately, the ketene ligand can be dis-

placed by CO, regenerating the starting carbonyl

complex, thus closing the catalytic cycle. In an earlier

publication [1], we have reported that Fe(CO)₃(PMe₃)₂

or Fe(CO)₃(PEt₃)₂were not suitable catalysts for the

process owing to their poor reactivity towards oxidative

addition reactions with alkyl halides. The ruthenium or

iron dicarbonyl complexes Ru(MeP(CH₂CH₂PMe₂)₂)-

(CO)₂, Ru(MeP(CH₂CH₂CH₂PMe₂)₂)(CO)₂, and Fe (MeP-

A catalytic metal mediated build-up of ketene moie-

ties is currently under investigation in our group [1].

The process involves a metal carbonyl catalyst and is

based on initial oxidative addition of an alkyl halide fol-

lowed by a CO insertion step. Subsequent deprotonation

*

Corresponding author. Tel.: +41 1 635 46 80; fax: +41 635 68 02.

E-mail address: hberke@aci.unizh.ch (H. Berke).

doi:10.1016/j.jorganchem.2004.11.055

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P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

(CH₂CH₂CH₂PMe₂)₂)(CO)₂, bearing strong donor tri-

dentate phosphine ligands, expectedly showed a much

higher reactivity towards oxidative additions. In con-

junction with these systems, problems were also encoun-

tered here for the reactions with CO or for the

deprotonation reactions. Deprotonation of the acetyl

species [Ru(COMe)(MeP(CH₂CH₂CH₂PMe₂)₂)(CO)₂]I

could not be eﬀected with P[MeN(CH₂)₃NMe]-

(NEt₂)(Nt-Bu) (BEMP) or even stronger bases such as

sodium hexamethyldisilazide (HMDS) or lithium diiso-

propylamide (LDA). It is assumed that the low acidity

of the acetyl complex arises from a too electron-rich me-

tal fragment bearing the acetyl group. Therefore, an

electronic tuning of the triphosphine ligand was under-

taken to enhance the acidity of the M-COCH₃protons

without losing on the ability of the metal center to

accomplish oxidative additions. The ruthenium and iron

complexes 1–8 bearing the novel tridentate phosphine li-

gands I–IV with terminal alkoxy groups were investi-

gated and the results are presented hereafter.

by a variety of methods [21–26] are restricted by the

reactivity of the internal tertiary phosphine function,

which readily quaternizes in the presence of P–Cl bonds.

Protecting groups such as BH₃or sulfur cannot be envis-

aged because of the alcoholysis conditions (tertiary

amine base are typically used to deprotect phosphine

borane adducts) [27–29] or the desulfuration conditions,

respectively. We therefore envisaged next the synthesis

of the trimethylene-bridged phosphine ligands from cou-

pling of a primary phosphine with allylphosphonites

which can be readily prepared from alcoholysis of ally-

ldichlorophosphine. The synthetic approach should also

be convenient for the synthesis of ethylene-bridged tri-

phosphines RP[CH₂CH₂P(OR)₂]₂by using vinylphosph-

onites, but the required vinyldichlorophosphine

intermediate is diﬃcult to prepare [30]. The reaction of

PCl₃with vinyltin derivatives failed to give dichlorovi-

nylphosphine [31]. In contrast to this, allyldichlorophos-

phine was available from allyltributyltin and PCl₃[32].

The reaction was carried out with irradiation and found

to be faster in the presence of a radical initiator (AIBN),

therefore a radical character of the substitution was pro-

posed. However, the reaction was reported [33] later to

also proceed without photolysis and in the presence of

duroquinone or acrylonitrile. Thus, an anionic process

cannot be excluded. We observed that the reaction of

allyltributyltin and PCl₃, carried out on the pure com-

pounds at room temperature and without irradiation,

proceeded cleanly to aﬀord high yields of allyldichloro-

phosphine (Scheme 1).

A slight excess of the allyltin derivative was always

used to ensure complete conversion of PCl₃into the

allylphosphine, because the two chloro phosphines are

diﬃcult to separate. Tributyltinchloride is regenerated

during the reaction and may be re-used. Conversion of

allyldichlorophosphine to dimethyl- or diisopropyl-

allylphosphonite [34] by alcoholysis with methanol or

isopropanol, respectively, in the presence of triethyl-

amine proceeded in excellent yields (Scheme 2).

The AIBN catalysed free radical addition [35–38] of

phenylphosphine or cyclohexylphosphine with either di-

methyl- or diisopropylallylphosphonite aﬀorded the tri-

phosphine ligands I–IV in quantitative yields

(Scheme 3).

2. Preparation of the tridentate phosphine ligands I–IV

The polyphosphines containing terminal alkoxy

groups provide chelating ligands with stronger p-accept-

ing properties than polyphosphines containing terminal

alkyl groups [2–4], owing to the greater electronegativity

of the alkoxy substituents [5]. Essentially two methods

have been applied to introduce alkoxy substituents on

a phosphorus atom: the alcoholysis of aminophosphine

derivatives [6–10] or the reaction of chlorophosphine

derivatives with an alcohol in the presence of a tertiary

amine base [11–15]. Triphosphine ligands of the type

RP[CH₂CH₂CH₂P(OR)₂]₂have not been reported pre-

viously. The tridentate phosphine ligands RP[CH₂-

CH₂P(OMe)₂]₂(R = Me, Ph), prepared from alcoholysis

of aminophosphine intermediates, have been reported

by King and Masler [7]. The procedure involves a base

catalysed addition [2,3,16,17,7] of dimethylvinylphosph-

onite to methyl- or phenylphosphine. The required vinyl

phosphonite intermediate was obtained from the reac-

tion of bis(dimethylamino)vinylphosphine with metha-

nol. We have however observed that substitution of

both amino groups did not occur when isopropanol

was used instead of methanol, presumably owing to ste-

ric factors. Thus, the synthetic method is not suitable for

triphosphines bearing terminal isopropoxy groups,

which are valuable ligands, since they should be less sen-

sitive to Arbuzov [18,19] type reactions than the triphos-

phines possessing methoxy groups. The conversion of

the P–Cl bonds in chlorophosphine derivatives appears

to have a wider scope than the alcoholysis of amino-

phosphines [20]. Approaches involving bis(primaryphos-

phine) derivatives of the type RP[CH₂CH₂CH₂PH₂]₂,

where the P–H bonds can be converted to P–Cl bonds

PCl₃

Sn(n-Bu)₃

PCl₂

MgX

Cl Sn(n-Bu)₃

Scheme 1.

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1431

OR'

OMe

MeOH

P

Ru

P

OMe

NEt₃

CO

Toluene, reflux 4d

Ru₃(CO)₁₂

R

P

PCl₂

I-IV

O(i-Pr)

P

i-PrOH

OR'

NEt₃

Scheme 2.

R

R'

Ph i-Pr

Cy i-Pr

Ph Me

Cy Me

1

2

3

4

hν

P(OR')₂

RPH₂

+

2

(R'O)₂P

PR

P(OR')₂

AIBN (cat.)

Scheme 4.

I

(R = Ph; R' = i-Pr)

The thermal reaction of Fe(CO)₅and the triphos-

phine ligands I or III aﬀorded the corresponding iron

tricarbonyl complexes 9 and 10, respectively, where the

triphosphine is g²coordinated together with minor

amounts of the target iron dicarbonyl complexes (5 or

7). The iron tricarbonyl complexes could also be ob-

tained by displacement of the cyclooctatetraene moiety

from Fe(COT)(CO)₃(Scheme 5).

Attempts to displace a carbonyl group by further

heating were not successful. It was observed that the

iron tricarbonyl complexes 9 and 10 could be converted

to the corresponding dicarbonyl complexes 5 and 7,

respectively, upon irradiation, however, in these cases

the reactions showed considerable amounts of decom-

position products. When a toluene solution of iron

pentacarbonyl is irradiated in the presence of the tri-

dentate phosphine ligands I–IV, complexes 5 and 7

are formed in similar yields. ³¹P NMR monitoring of

the photochemical reactions according to Scheme 5

showed that the iron dicarbonyl complexes were the

only compounds present along with the free phosphine

ligands after 4–6 h. Complete decomposition occurred

upon longer irradiation times (10 h or more). The syn-

thesis of the iron dicarbonyl complexes (5–8) from the

reduction of the corresponding Fe(II) precursors was

II (R = Cy; R' = i-Pr)

III (R = Ph; R' = Me)

IV

(R = Cy; R' = Me)

Scheme 3.

The irradiation was carried out on the pure interme-

diates and the ligands were obtained as colourless

air-sensitive viscous liquids, which gave satisfactory

elemental microanalysis. The NMR spectra were in ac-

cord with the given structures [39–41]. The compounds

solidiﬁed upon storing at ꢀ30 ꢁC.

3. Preparation of the Ru(0) and Fe(0) dicarbonyl

complexes 1–8

Only a few reports of ruthenium complexes contain-

ing tridentate phosphine ligands have appeared in the

literature [42–44]. Synthetic access to them involve either

direct substitution on zerovalent ruthenium carbonyl

complexes [45] or reduction of ruthenium(II) precursors

in the presence of carbon monoxide [44,46,47]. The com-

plexes 1–4 were prepared in good yields from the ther-

mal reaction of the corresponding tridentate phosphine

ligand with Ru₃(CO)₁₂in reﬂuxing toluene (Scheme 4).

The ruthenium dicarbonyl complexes 1–4 were all ob-

tained as air-sensitive light yellow solids, which gave sat-

isfactory elemental analysis. All complexes were fully

characterized by IR and NMR spectroscopy.

In general, carbonyl complexes of iron (Fe(CO)₅,

Fe₂(CO)₉and Fe₃(CO)₁₂) react with monodentate phos-

phine ligands to give mixtures of the mono- and di-

substituted derivatives [Fe(CO)₄L] and [Fe(CO)₃L₂]

[48,49]. This behaviour is expected to result from the

intermediary [Fe(CO)₄] [50,51]. Multidentate phosphine

ligands allow substitution of three CO groups. Alterna-

tively, tri(tertiary phosphine)dicarbonyliron(0) com-

plexes are often prepared by reduction of iron(II)

precursors [52–54].

examined next. FeCl₂reacted with

I

to give

Fe(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)Cl₂(11) in high yield.

The compound showed satisfactory elemental analysis.

However, an attempted reduction of 11 with sodium

amalgam did not lead to the dicarbonyl complex 5 pre-

sumably owing to the poor solubility of 11 in THF.

Therefore, the analogous more soluble diiodo complex

Fe(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)I₂(12) was prepared

in high yield from FeI₂and I in THF at room temper-

ature. Complex 12 was cleanly reduced to the target

complex 5 under an atmosphere of CO with sodium

naphthalenide. A similar procedure could be applied

for the synthesis of 6 (Scheme 6).

Surprisingly, the iron complexes 7 and 8 bearing the

tridentate phosphine ligands III and IV with terminal

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P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

OR

P

CO

h , 4-6 h

ν

Ph

P

Fe

P

Fe(CO)₅

CO

I or III

5 (R = i-Pr)

7 (R = Me)

OR

hv

OR

P

CO

∆

Fe(COT)(CO)₃

Ph

P

Fe

I or III

CO

9 (R = i-Pr)

10 (R = Me)

(RO)₂P

Scheme 5.

OR'

P

Fe

P

Fe

P

CO

1. Triphosphine I or II, THF

Triphosphine III or IV

Toluene, hν 4-6 h

R

P

R

P

FeI₂

Fe(CO)₅

2. Sodium naphthalenide

-78˚ -> r.t

OR'

7 (R = Ph, R' = Me)

8 (R = Cy, R' = Me)

5 (R = Ph, R' = i-Pr)

6 (R = Cy, R' = i-Pr)

Scheme 7.

Scheme 6.

methoxy groups could not be prepared using a similar

approach as for the synthesis of 5 and 6. Brunnet et

al. [55] published an extensive series of Fe(CO)₂L₃com-

plexes (L = phosphine, phosphite) involving a one-pot

reaction of K[FeH(CO)₄] and the corresponding ligands

in a protic medium. The type of complexes Fe-

(CO)₂(PR₃)₃and Fe(CO)₂(P(OR)₃)₃were obtained in

fair to high yields (depending on the ligandꢀs cone an-

gle). However, preparations of 7 or 8 starting from

K[FeH(CO)₄] [56–58] or H₂Fe(CO)₄[59,60] failed. The

Fe(0) dicarbonyl complexes 7 and 8 were ﬁnally ob-

tained in low yields (ꢁ30%) from the short time irradia-

tion of Fe(CO)₅with the tridentate phosphine III and

IV, respectively (Scheme 7). ³¹P NMR monitoring of

the reaction showed the optimum irradiation times for

the reaction to be 4–6 h in dilute toluene solutions

(0.1 M) of Fe(CO)₅and the respective triphosphine li-

gand. Irradiation was stopped as soon as other uniden-

tiﬁed broad signals started to appear around 35 and

220 ppm in the ³¹P NMR spectrum.

4. X-ray diﬀraction studies on 1, 3 and 5

Suitable crystals for X-ray diﬀraction for 1, 3 and 5

were obtained from slow cooling of saturated toluene

solutions to ꢀ30 ꢁC. Selected bond distances (A) and

˚

bond angles (ꢁ) are listed in Table 1. The complexes pos-

sess approximate trigonal bipyramidal geometry with

the tridentate phosphine ligand spanning axial–equato-

rial–axial positions (Figs. 1–3). Axial distortions are

more pronounced for the complexes bearing dii-

sopropylphosphonite groups (1 and 5). The phosphonite

groups located above the equatorial plane are eclipsed

with those located below the equatorial plane. With re-

spect to the P(2)–P(3) axis, the phosphonite groups and

the equatorial carbonyl ligands appear staggered. The

longest phosphine–metal bond is obtained for the equa-

torial phosphine P(1). This bond length pattern is in ac-

cord with the well-established fact [61] that r-donor

ligands are bound weakest in the equatorial positions

in d⁸trigonal bipyramids.

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1433

Table 1

5. Reaction of 1–8 with alkyl iodides

˚

Comparison of selected related bond lengths (A) and bond angles (ꢁ) in

1, 3 and 5

The oxidative additions of MeI to the ruthenium cen-

ters of 1–4 are completed within 5 min when the reac-

tions are performed in dichloromethane at room

temperature. Under the same conditions, the reactions

of the iron complexes 5 and 7 bearing ligands with a

phenyl group on the internal phosphorus atom of the

triphosphine take 48 h. Consistent with the increased

basicity of the cyclohexyl triphosphine system, the iron

complexes 6 and 8 react on a qualitative scale faster with

MeI in comparison with the phenyl-substituted com-

pounds. Furthermore, the ruthenium complexes react

much faster with MeI than the iron complexes. A similar

trend has been observed for the disubstituted phosphine

derivatives of Ru(CO)₅and Fe(CO)₅[62–66]. The oxida-

tive addition reactions of MeI with 1–8 are summarized

in Scheme 8.

1 (M = Ru)

3 (M = Ru)

5 (M = Fe)

˚

Bond distances (A)

M(1)–P(1)

M(1)–P(2)

M(1)–P(3)

M(1)–C(1)

M(1)–C(2)

C(1)–O(1)

C(2)–O(2)

2.3608(6)

2.2918(6)

2.3025(6)

1.905(3)

1.888(2)

1.154(3)

1.166(3)

2.352(2)

2.268(2)

2.261(2)

1.918(8)

1.921(8)

1.149(10)

1.185(11)

2.2203(6)

2.1601(6)

2.1630(6)

1.7537(18)

1.747(2)

1.169(2)

1.173(2)

Angles (ꢁ)

P(1)–M(1)–P(2)

P(1)–M(1)–P(3)

P(2)–M(1)–P(3)

P(1)–M(1)–C(1)

P(1)–M(1)–C(2)

C(1)–M(1)–C(2)

C(1)–M(1)–P(2)

C(1)–M(1)–P(3)

C(2)–M(1)–P(2)

C(2)–M(1)–P(3)

89.62(2)

88.99(2)

171.46(2)

96.62(8)

142.20(8)

121.17(11)

93.19(8)

95.35(8)

87.81(8)

88.12(8)

95.72(8)

86.18(8)

177.23(8)

105.3(3)

122.2(3)

132.5(4)

91.2(3)

91.42(2)

90.40(2)

169.35(2)

96.96(7)

144.93(6)

118.11(9)

93.85(6)

96.34(6)

86.06(6)

86.41(6)

86.3(3)

84.8(2)

95.9(2)

An isomeric mixture of the corresponding mer,trans-

and mer,cis-[M(Me)(triphos)(CO)₂]I (M = Fe, Ru; tri-

phos = I–IV) cationic octahedral complexes is formed.

Fig. 1. Model of the structure of 1. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are shown with a 30% probability level.

1434

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

Fig. 2. Model of the structure of 3. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are shown with a 30% probability level.

¹H NMR monitoring of the reactions shows that the

trans CO isomers 13a–20a are formed. Some of these

complexes, seen in a most prominent way for 17a and

19a, are slowly converted further in an equilibration

reaction to the corresponding cis CO isomers 13b–20b.

Similar observations have been made on the related

ruthenium complexes [Ru(Me)(PhP(CH₂CH₂CH₂P-

Cy₂)₂(CO)₂]I [43] and [Ru(Me)(MeP(CH₂CH₂CH₂P-

Me₂)₂(CO)₂]I [1]. The isomerisation process was

observed to occur faster with the iron complexes than

with the ruthenium complexes. For a given metal (Ru

or Fe), the isomerisation also proceeds faster for the

complexes bearing a phenyl substituent instead of the

cyclohexyl on the internal phosphorus atom of the tri-

dentate phosphine ligand. For example, the oxidative

addition of MeI to 5 is completed in 48 h at room tem-

perature with concomitant equilibration to the cis CO

isomer 17b. However, reaction of 6 with MeI aﬀords

the equilibrium mixture of the isomers 18a/18b only

after ﬁve days of equilibrium at room temperature. It

is remarkable that for all the cyclohexyl derivatives the

trans isomers (14a, 16a, 18a and 20a) are more stable,

while for the phenyl derivatives the same is valid for

M = Ru (13a and 15a), but in the cases of M = Fe

(17b and 19b) there is an inverse preference.

Complexes 13a–20b were structurally assigned on the

basis of IR and NMR spectroscopic data of the isomeric

mixtures in solution. The IR spectra of the mer,trans-

[M(Me)(triphos)(CO)₂]I complexes (13a–20a, M = Ru,

Fe; triphos = I–IV) are characterized by a single strong

m(CO) stretching band. This supports the trans disposi-

tion of the carbonyl ligands in these octahedral com-

plexes. The ³¹P NMR spectra indicate a meridional

arrangement of the tridentate phosphine ligand in the

complexes. The spectra show an AM₂spin system with

a triplet resonance for the internal phosphorus nucleus

and a doublet resonance for the terminal phosphonite

moieties. The H NMR spectra are consistent with the

proposed structures. The Me_Rumoieties exhibit doublet

of triplet resonances.

The observation that the coupling constant to the

trans phosphorus nucleus is smaller than the coupling

to the cis phosphorus nuclei has precedence from related

observations in the literature. A similar trend was re-

ported on ruthenium complexes [42,43,67]. The reso-

nance for the metal bound methyl group also appeared

as doublet of triplets in the ¹³C NMR spectra. mer,

1

trans-Derivatives showed in some cases a greater

tendency for crystallisation. Thus, it was possible to

obtain suitable crystals for X-ray diﬀraction for 13a

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1435

Fig. 3. Model of the structure of 5. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are shown with a 30% probability level.

+

OR'

P

M

P

M

P

M

P

Me

CO

OC

MeI

CO

R

P

R

P

R

P

CO

Me

-

I

OR'

I

OR'

R

R'

M

Ph i-Pr

Cy i-Pr

Ph Me

Cy Me

1

2

3

4

Ru

13a - 90%

14a - 100%

15a - 98%

16a - 100%

13b - 10%

14b - Traces

15b - 2%

16b - Traces

Ph i-Pr

Cy i-Pr

Ph Me

Cy Me

Fe

5

6

7

8

17a - Traces

18a - 95%

19a - Traces

20a- 100%

17b - 100%

18b - 5%

19b - 100%

20b - Traces

Scheme 8.

and 21. Suitable crystals for 13a were obtained by

slow cooling of a saturated dichloromethane solution

to ꢀ30 ꢁC. The structure is shown in Fig. 4. Selected

The X-ray diﬀraction study reveals a pseudo octahe-

dral geometry at ruthenium, with a meridionally ar-

ranged triphosphine ligand and trans carbonyl groups.

The structure of 20a was also unequivocally estab-

lished by a single crystal X-ray diﬀraction study on the

˚

bond distances (A) and bond angles (ꢁ) are listed in

Table 2.

1436

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

Fig. 4. Model of the structure of 13a. Hydrogen atoms and iodine counter ion are omitted for clarity. Thermal ellipsoids are shown with a 30%

probability level.

Table 2

the methyl group is located trans to the internal phos-

phorus atom of the tridentate phosphine ligand. The

longest Fe–P distance is found for Fe(1)–P(1) trans to

the methyl ligand, while Fe(1)–P(2) and Fe(1)–P(3) have

comparable values.

The cis carbonyl complexes 13b–20b exhibit two

strong m(CO) bands in the IR spectra indicating that

the carbonyl ligands are disposed cis to each other in

the octahedral complexes. The ³¹P NMR spectra consist

of a triplet and doublet resonance pattern and support

the meridional arrangement of the tridentate ligands

around the metal center.

˚

Selected bond lengths (A) and bond angles (ꢁ) in 13a

˚

Bond distance (A)

Angle (ꢁ)

Ru(1)–C(3)

Ru(1)–P(1)

Ru(1)–P(2)

Ru(1)–P(3)

Ru(1)–C(1)

Ru(1)–C(2)

C(1)–O(1)

C(2)–O(2)

2.225(14)

2.377(3)

2.335(3)

2.345(3)

1.919(15)

1.934(15)

1.132(15)

1.151(15)

P(1)–Ru(1)–C(3)

P(2)–Ru(1)–P(3)

C(1)–Ru(1)–C(2)

P(1)–Ru(1)–C(1)

P(1)–Ru(1)–C(2)

C(1)–Ru(1)–C(3)

C(2)–Ru(1)–C(3)

C(1)–Ru(1)–P(2)

C(1)–Ru(1)–P(3)

C(2)–Ru(1)–P(2)

C(2)–Ru(1)–P(3)

C(3)–Ru(1)–P(2)

C(3)–Ru(1)–P(3)

175.8(4)

177.10(12)

172.2(5)

89.0(3)

98.4(4)

86.9(5)

85.7(5)

92.4(4)

88.8(4)

89.8(4)

88.6(4)

88.8(3)

6. Reactions with I₂and the alkyl iodides EtI, n-PrI

and i-PrI

corresponding tetraphenylborate salt (21) (Fig. 5). Suit-

able crystals were obtained by slow cooling of a satu-

rated dichloromethane solution of 21 to ꢀ30 ꢁC.

The oxidative addition of alkyl iodides (EtI, n-PrI

and i-PrI) to the ruthenium and iron complexes 1–8

did not produce the expected alkyl metal complexes. It

is interesting to note that the oxidative addition of

MeI to RuL₂(CO)₃(L = phosphine) does even not take

place when the phosphine ligand is diﬀerent from

PMe₃[68–70]. No reactions were also observed with

MeI when the starting compound Fe(CO)₃L₂contained

˚

Selected bond distances (A) and bond angles (ꢁ) are

listed in Table 3.

The cation of 21 adopts a pseudo octahedral geome-

try. The triphosphine ligand is meridionally arranged

around the metal atom. The structure conﬁrms that

the carbonyl ligands occupy trans positions and that

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1437

Fig. 5. Model of the structure of 21. Hydrogen atoms and the BPh^ꢀ₄counter ion are omitted for clarity. Thermal ellipsoids are shown with a 30%

probability level.

Table 3

Oi-Pr

+

˚

Selected bond lengths (A) and bond angles (ꢁ) in 21

˚

Bond distance (A)

P

M

P

M

P

Angle (ꢁ)

CO

OC

RI (R = Et, n-Pr, i-Pr)

CO

Fe(1)–C(3)

Fe(1)–P(1)

Fe(1)–P(2)

Fe(1)–P(3)

Fe(1)–C(1)

Fe(1)–C(2)

C(1)–O(1)

C(2)–O(2)

2.105(5)

P(1)–Fe(1)–C(3)

P(2)–Fe(1)–P(3)

C(1)–Fe(1)–C(2)

P(1)–Fe(1)–P(2)

P(1)–Fe(1)–P(3)

P(1)–Fe(1)–C(1)

C(3)–Fe(1)–P(2)

C(3)–Fe(1)–P(3)

C(3)–Fe(1)–C(1)

C(3)–Fe(1)–C(2)

C(1)–Fe(1)–P(2)

C(1)–Fe(1)–P(3)

C(2)–Fe(1)–P(2)

C(2)–Fe(1)–P(3)

175.64(12)

177.54(5)

167.66(17)

91.07(4)

R

P

or I₂

R

P

2.2724(10)

2.2097(10)

2.2159(10)

1.832(4)

I

-

Oi-Pr

I

Oi-Pr

87.93(4)

1.789(3)

1.079(4)

1.135(4)

91.94(12)

89.21(11)

91.96(12)

83.70(16)

84.11(16)

92.35(12)

89.92(12)

89.34(11)

88.63(11)

M

R

M

R

1

2

5

6

Ph

Cy

Ph

Cy

Ph

Cy

Ph

Cy

Ru

Fe

22

Ru

Fe

23

26

27

Scheme 9.

dent of the type of alkyl iodide used. The same products

were obtained from the oxidative addition reaction of a

stoichiometric amount of I₂to the zero valent com-

plexes, which proceeds instantaneously in dichlorome-

thane at room temperature (Scheme 9).

The structures of the iodo complexes (22, 23, 26 and

27) were established by spectroscopic means. Further-

more iodo complex 22 could be characterized by an X-

ray diﬀraction study. The complex was crystallized from

the reaction mixture of 1 with i-PrI (Fig. 8). Similar

triethylphosphine instead of trimethylphosphine [71].

This behaviour may be due to a notable steric hindrance

of the ligand on the oxidative addition process.

The complexes bearing triphosphine ligands with ter-

minal isopropoxy groups (1, 2, 5 and 6) react within one

week with an excess of EtI, n-PrI or i-PrI in CH₂Cl₂at

room temperature to aﬀord an iodo complex indepen-

1438

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

observations [64] have been made in the reaction of alkyl

halides with Fe(CO)₃L₂(L = PMe₃, PPh₃) which pro-

duced Fe(CO)₂L₂I₂species. It has been shown that the

reactions involve an initial step in which halogen radi-

cals are formed from the alkyl halides either photochem-

ically or thermally. These radicals react with Fe(CO)₃L₂

in an one-electron oxidation to give the radical cation

[Fe(CO)₃L₂]^Å+as shown for the reaction of halogens

with Fe(CO)₃L₂[72].

A further complication was observed for the com-

plexes bearing ligands with terminal dimethylphospho-

nite groups. Reaction of EtI, n-PrI or i-PrI with 3, 4, 7

or 8 therefore also led to the corresponding iodo com-

plexes (24, 25, 28 and 29, respectively) but also to addi-

tional products corresponding to the oxidative addition

of MeI (15a, 16a, 19a and 20a, respectively) (Scheme

10).

The iodo complexes 22–29 were structurally assigned

on the basis of IR and NMR data. Furthermore, the

structure of 22 was unequivocally established by a single

crystal X-ray diﬀraction study (Fig. 6). Suitable crystals

were obtained by slow cooling of a saturated dichlorom-

ethane solution of 22 to ꢀ30 ꢁC. Selected bond distances

˚

(A) and bond angles (ꢁ) are listed in Table 4.

The X-ray study conﬁrms that 22 is an iodo complex.

The cationic complex adopts an octahedral geometry

with an iodide counter anion. The triphosphine ligand

is meridionally arranged around the metal center. The

structure shows that a carbonyl ligand is in trans posi-

tion to the internal phosphorus atom of the triphosphine

ligand and consequently the iodide is found trans to a

carbonyl ligand. The Ru–I distance is consistent with

such separations in other ruthenium iodo complexes

[74].

Although phosphine oxide moieties could not be de-

tected by ³¹P NMR spectroscopy, MeI is obviously gen-

erated from an Arbuzov type reaction at the

coordinated –P(OMe)₂groups of the tridentate phos-

phine ligands. Similar Arbuzov reactions were observed

at the coordinated trimethylphosphite groups in the

complex [CpCo(dppe)P(OMe)₃] [73]. Consistent with

the eﬀect of increased sterics on Arbuzov reactions the

highest amounts of methyl complexes were observed

with EtI (6–8% by ³¹P NMR spectroscopy) while only

traces could be detected by ¹H NMR spectroscopy when

i-PrI was used in the oxidative addition reactions. As

observed for the oxidative addition reactions of MeI

with 3, 4, 7 and 8, isomerisation of the trans CO methyl

complexes (15a, 16a, 19a and 20a) to the corresponding

cis CO isomers (15b, 16b, 19b and 20b) could be ob-

served in the cases where the concentration of the

7. Reactions with CO and deprotonation reactions

When 1–8 are reacted with MeI and the resulting iso-

meric mixtures of the methyl complexes (13a/b–20a/b)

are stirred under 1 bar of carbon monoxide for 48 h.

In all cases, the same single acetyl complex is obtained

(Scheme 11).

This reactivity towards CO insertions parallels earlier

observations on related ruthenium complexes and has

been discussed previously [1]. The presence of the acetyl

moiety is conﬁrmed by IR spectroscopy. The corre-

sponding m(C@O) vibration is found as a band of med-

ium intensity in the range between 1604 and 1616 cm^ꢀ1

and further evidence for the presence of trans CO groups

is provided by the appearance of one strong carbonyl

absorption. The acetyl moieties are also indicated in

1

methyl complexes were suﬃcient to be detected by H

or ³¹P NMR spectroscopy (essentially for the reactions

with EtI).

1

the H NMR spectra giving rise to singlet resonances

(d 2.4–2.7 ppm) for the acetyl protons. The ³¹P NMR

I₂

+

OMe

P

M

P

M

P

CO

OC

Me

OC

RI (R = Et, n-Pr, i-Pr)

CO

R

P

M

P

+

R

P

R

P

I

CO

-

OMe

I

-

OMe

I

OMe

M

R

3

4

7

8

Ru

Fe

Ph

Cy

Ph

Cy

24

25

28

29

15a

16a

19a

20a

Scheme 10.

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1439

Fig. 6. Model of the structure of 22. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are shown with a 30% probability level.

Table 4

R

R'

+

M

˚

Selected bond lengths (A) and bond angles (ꢁ) in 22

˚

Bond distance (A)

OR'

Ph i-Pr

Cy i-Pr

Ph Me

Cy Me

Ru

30

31

32

33

Angle (ꢁ)

P

M

P

Ru(1)–I(1)

Ru(1)–P(1)

Ru(1)–P(2)

Ru(1)–P(3)

Ru(1)–C(1)

Ru(1)–C(2)

C(1)–O(1)

C(2)–O(2)

2.7582(7)

2.3997(17)

2.350(2)

1.890(7)

1.949(7)

1.125(9)

1.119(8)

P(1)–Ru(1)–C(2)

P(2)–Ru(1)–P(3)

I(1)–Ru(1)–C(1)

P(1)–Ru(1)–P(2)

P(1)–Ru(1)–P(3)

P(1)–Ru(1)–C(1)

P(1)–Ru(1)–I(1)

I(1)–Ru(1)–P(2)

I(1)–Ru(1)–P(3)

I(1)–Ru(1)–C(2)

C(1)–Ru(1)–C(2)

C(1)–Ru(1)–P(2)

C(1)–Ru(1)–P(3)

C(2)–Ru(1)–P(2)

C(2)–Ru(1)–P(3)

171.6(2)

178.35(6)

177.6(2)

89.18(7)

89.79(7)

95.3(2)

COMe

OC

1. MeI

2. CO

1-8

R

P

CO

Ph i-Pr

Cy i-Pr

Ph Me

Cy Me

Fe

34

35

36

37

-

OR'

I

87.05(4)

89.93(5)

88.73(5)

84.6(2)

Scheme 11.

¹³C NMR spectrum, the singlet resonance for the acetyl

methyl group is found at around d 50 ppm, and the

¹³CO resonance is found at expected much lower ﬁeld

(d 259–268 ppm) as a doublet of triplets in cases where

the signal could be resolved. The splitting pattern is con-

sistent with the acetyl moiety disposed trans to the inter-

nal phosphorus nucleus of the tridentate phosphine

ligand, since the latter is meridionally arranged around

the metal center. The carbonyl ligands usually exhibited

broad resonances in the region of d 200–210 ppm. In the

case of 31, the CO ligands give rise to a quartet reso-

nance, showing the magnetic equivalence of all three

93.1(3)

89.7(3)

91.7(3)

90.7(3)

90.1(3)

spectra of the acetyl complexes consist of an AM₂sys-

tem with a triplet resonance for the internal phosphorus

atom of the triphosphine and a doublet resonance for

the terminal phosphorus atoms, which suggests the gi-

ven meridional phosphorus substitution pattern. In the

1440

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

phosphorus ligands and an isochronous behaviour of

the two ¹³C nuclei. In the case of 34, two signals for

the two trans carbonyl groups were found as two distinct

doublets of triplets. This is attributed to the rigid stereo-

chemistry at the internal phosphorus atom of the tri-

phosphines inducing distinction of the environments of

the CO groups.

on the internal phosphorus atom of the triphosphine li-

gand (34 and 36) and 40 h for those having a cyclohexyl

substituent (35 and 37). Under the same reaction condi-

tions, the ruthenium acetyl complexes 30–33 reacted

much slower and the reaction was not completed even

after 4 days. It is noteworthy that the use of the stronger

base sodium hexamethyldisilazide (HMDS) eﬀected

instantaneous deprotonation of the ruthenium or iron

acetyl complexes when the reaction was carried out in

dichloromethane at room temperature. In all the depro-

tonation experiments, however, the products of the reac-

tions of the acetyl complexes with either BEMP or

HMDS were identiﬁed spectroscopically as the ‘‘start-

ing’’ zero valent dicarbonyl metal complexes 1–8

(Scheme 12).

It should be noted that when the iron acetyl complex

34 was subjected for 48 h to the same conditions as those

employed in the deprotonation reactions with BEMP

(acetonitrile, reﬂux, CO atmosphere) in the absence of

a base, the species proved to be stable apart from the

traces of a decarbonylation product. This indicates that

generation of the zero valent metal complex 5 from the

corresponding acetyl complex does not occur in the ab-

sence of the base and rules out its formation from a

decomposition pathway of the parent acetyl species.

However, despite that any ketene product could logi-

cally appear in Scheme 12 it was not possible to trace any

ketene complex intermediate regardless whether the

deprotonations were carried out under forcing condi-

tions or at room temperature. It is also diﬃcult to verify

whether ketene complexes do form, but replacement of a

8. Deprotonation experiments

In order to access ketene complexes, deprotonation

of the acetyl complexes 30–37 was attempted using

BEMP as the base. The initial deprotonation experi-

ments carried out in dichloromethane at room tempera-

ture and under a carbon monoxide atmosphere showed

that no reaction occurred with the ruthenium acetyl

complexes (30–33) and that the iron acetyl complexes

(34–37) reacted very slowly as evidenced by the presence

of a small amount of protonated BEMP in the ³¹P NMR

spectra after four days of reaction. The deprotonation

experiments with BEMP can be conveniently monitored

by ³¹P NMR spectroscopy. The signal of the protonated

base [BEMPH]I appears at d 23 ppm, whereas the

BEMP exhibits a resonance at d 1 ppm. The dichlorom-

ethane was changed for acetonitrile and the deprotona-

tion experiments with BEMP were carried out at reﬂux

temperature of the solvent under an atmosphere of CO

with ³¹P NMR monitoring. Under these conditions,

the deprotonation reactions were completed after 24 h

for the iron acetyl complexes bearing a phenyl group

+

OR'

P

COMe

OC

CO

CO (1 atm.)

M

P

R

P

M

P

R

P

CO

-

BEMP, CH₃CN reflux

OR'

I

or HMDS, CH₂Cl₂, room temp.

OR'

30-37

1-8

+ CO

- CO

M

R

R'

OR'

+

P

M

P

Ru

1

2

3

4

13b

14b

15b

16b

30

31

32

33

Ph iPr

Cy iPr

Ph Me

Cy Me

CO

OC

P

R

Me

OR'

Fe

Ph iPr

Cy iPr

Ph Me

Cy Me

5

6

7

8

17b

18b

19b

20b

34

35

36

37

-

I

13b-20b

Scheme 12.

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1441

ketene ligand would anyway be expected to occur readily

in the presence of carbon monoxide. When the deproto-

nation experiments were carried out under a nitrogen

atmosphere decarbonylation of the acetyl complexes

was observed in most cases, which conﬁrms that the

deprotonations of the acetyl moieties are slow reactions,

signiﬁcantly slower than the decarbonylation steps.

While deprotonation of the acetyl moieties become

plausible by the appearance of the protonated BEMP

resonance in the ³¹P NMR spectra, it is likely that the

intermediate ketene complexes are not stable and can

therefore not be traced spectroscopically. In order to

pursue the fate of any ketene product, labelling experi-

ments with the D and ¹³C labeled iron acetyl complexes

38 and 39 were carried out. These complexes were pre-

pared from the reaction of 5 with CD₃I and ¹³CH₃I,

respectively, followed by the reaction with natural abun-

dance ¹²CO. The deprotonation experiments of 38 and

39 with BEMP were pursued by ²H, ¹³C and ³¹P

NMR spectroscopy and the results are summarized in

Scheme 13.

After 24 h of reaction in reﬂuxing acetonitrile and un-

der an atmosphere of CO, the ²H NMR spectrum shows

that 38 is no longer present in the reaction mixture as

evidenced by the complete disappearance of the singlet

resonance at d 2.6 ppm corresponding to the Fe-COCD₃

moiety. Only one singlet resonance at d 1.5 ppm can be

observed in the ²H NMR spectrum. This resonance

actually corresponds to the signal of the deuterated

base. The presence of [BEMPD]I is also conﬁrmed by

³¹P NMR spectroscopy with the observation of a singlet

resonance at 23 ppm and apart from minor amounts of

38 and 39, the ³¹P NMR spectrum indicates that 5 is the

predominant species. The ¹³C NMR spectrum conﬁrms

that only traces of the acetyl species remain (singlet res-

onance at d 48.5 ppm) and apart from some minor sig-

nals, no ¹³C resonance of signiﬁcant intensity is

observed. Evidence for the formation of diketene result-

ing from a dimerisation of ketene, was also not obtained

based upon the ¹³C NMR analysis. Throughout the

deprotonation experiments, the signals can be observed

of the labelled iron acetyl and methyl complexes. How-

2

After 28 h of reaction at room temperature, the iron

acetyl complexes 38 and 39 are the main species along

with small amounts of the decarbonylated species 40

and 41, while only traces of 5 can be detected in the

³¹P NMR spectroscopy (Fig. 7).

ever, while the H and ¹³C resonances of the acetyl spe-

cies gradually disappear, no signals for labelled species

2

appear as analysed both by H and ¹³C NMR spectros-

2

copy. In fact, the H experiment conﬁrms that the base

actually abstracts a proton from the Fe-COCD₃group,

as indicated by the formation of [BEMPD]I, and

supports the formation of the zerovalent ‘‘starting’’

dicarbonyl complex 5 via deprotonation of the corre-

sponding acetyl species with necessarily concomitant

formation of a ketene moiety. However, tracing of the

released ketene up to now remained unsuccessful and

its chemical fate is as yet unclear in these reactions.

In order to support a mechanistic scheme involving

free ketene species, an independent experiment with

the reaction of free ketene with BEMP was investigated.

Recently, BEMP was reported [75] to produce ketenes

from the dehydrohalogenation reaction of a variety of

acid chlorides. High yields of RHC@C@O (R = Br,

ethyl, phenyl, phenoxy, benzyloxy, 1-naphthyl, 2-naph-

thyl, 2-thienyl) were obtained when THF solutions of

the corresponding acid chlorides were passed through

a column packed with polymer-supported BEMP and

2

The H NMR spectrum shows an intense resonance

for the acetyl moiety of 38 at 2.6 ppm and a broad signal

at ꢀ0.2 ppm indicates the presence of a small amount of

40. The ¹³C NMR spectrum is consistent with the obser-

vations made from the ²H NMR spectrum. The labelled

carbon atom of the acetyl group of 39 exhibits a singlet

at 48 ppm and the presence of decarbonylated 39 is evi-

denced by the quartet resonance for 41 at ꢀ11 ppm. Fi-

nally, the presence of acetyl and methyl iron complexes

is conﬁrmed by ³¹P NMR, which also shows the pres-

ence of traces of 5 identiﬁed by the resonance at

216 ppm. Thus, signiﬁcant deprotonation of the acetyl

iron species with BEMP does not occur at room

temperature.

After 12 h in reﬂuxing acetonitrile, about half of the

iron acetyl complexes have reacted with BEMP and

the reaction is completed after 24 h (Fig. 8).

Oi-Pr

P

Oi-Pr

+

P

M

P

M

P

CO

COR

CO

OC

CO (1 atm.)

+ CO

- CO

Ph

P

M

P

Ph

P

Ph

P

R

CO

BEMP

CH₃CN reflux

-

Oi-Pr

I

Oi-Pr

38 (R = CD₃)

39 (R = ¹³CH₃)

5

40 (R = CD₃)

41 (R = ¹³CH₃)

Scheme 13.

1442

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

Fig. 7. NMR spectroscopy of the products of the deprotonation reaction of 38 and 39 with BEMP (28 h room temperature, CO atmosphere).

cooled to ꢀ78 ꢁC. Although the approach is believed by

the authors to be amenable to the formation of most

reactive ketenes, exclusively preparation of mono-

substituted ketenes was reported [76]. We have observed

that a reaction occurs when ketene and BEMP are

brought together, even at low temperatures. Ketene,

generated by the dehydrohalogenation [74] of acetyl

chloride with diisopropylethylamine (DIEA) catalysed

by a Lewis acid (Al(SbF₆)₃), was condensed into a

dichloromethane solution of BEMP cooled by means

of a dry ice/acetone bath. A ³¹P NMR spectrum of the

light yellow solution carried out at ꢀ80 ꢁC showed that

an adduct is formed with a sharp resonance at d 26 ppm.

The signal then quickly disappeared upon warming to

room temperature while the light yellow solution turned

brown and only a very broad resonance around d

33 ppm remained at 20 ꢁC. Heating to 80 ꢁC led to the

formation of an insoluble sticky material with no phos-

phorus resonances in the ³¹P NMR spectrum. It is pro-

posed that at ꢀ80 ꢁC, the ketene reacts with BEMP to

give a base-ketene adduct:

H

O

H

Me

N

^tBu

N

P

N

NEt₂

Me

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1443

Fig. 8. NMR spectroscopic analysis pursuit of the products of the deprotonation reaction of 38 and 39 with BEMP after a 24-h reﬂux period in

acetonitrile under an atmosphere of CO.

and 5) and -oscillation modes (for 3, 13a, 21 and 22)

were necessary for the increments of 1.0ꢁ, 1.0ꢁ and

Upon warming, the latter presumably undergoes further

reaction either with ketene or the ketene-BEMP adduct

1.2ꢁ, 1.0ꢁ, 0.9ꢁ, and 0.7ꢁ per exposure in each case. Total

exposure times were 19, 19, 22, 41, 27 and 28 h. The

itself, resulting in insoluble polymeric material. This all

prevented proper characterisation of any ketene released

intensities were integrated by using a dynamic peak pro-

in the deprotonation reactions of Schemes 12 and 13.

ﬁle analysis and estimated mosaic spread (EMS) check

was performed to prevent overlapping intensities. For

the cell parameter reﬁnements 7490 (13a) to 8000 reﬂec-

tions with intensities I > 6r(I) were selected out of the

whole limiting spheres for the six structures. A total of

34,297, 29,400, 33,723, 39,215, 49,145 and 34,289 reﬂec-

tions were collected, of which 9168, 6432, 8319, 16,330,

13,263 and 10,409 were unique after performing absorp-

tion corrections and data reductions (R_int= 4.90%,

14.60%, 7.22%, 20.27%, 13.51% and 8.86%). 15, 10,

13, 12, 7 and 8 indexed crystal faces were used for the

numerical absorption corrections [78].

9. X-ray structure analyses

The X-ray diﬀraction data were collected at measure-

ment temperatures of 123(2) K for 1, 153(2) K for 3, 5

and 22, and of 183(2) K for 13a and 21, using an imag-

ing plate detector system (Stoe IPDS) with graphite-

˚

monochromated Mo Ka-radiation (k = 0.71073 A). A

total of 200, 183, 190, 220, 205 and 209 images were

exposed at constant times of 1.50, 3.00, 1.80, 7.00,

3.00 and 2.60 min per image for the structures 1, 3, 5,

13a, 21 and 22 [77]. The crystal-to-image distances were

set to 50 mm for 1, 3, 5 and 21, and to 60 mm for 13a

and 22 (h_maxrange: 27.96–30.37ꢁ). /-rotation (for 1

All crystals were embedded in polybutene oil within a

glove box. The crystal quality was examined under

polarized light. Sometimes crystals with intrusions

1444

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

(holes or solvent) or with tiny intergrown pieces (3, 13a

and 21) had to be accepted for the X-ray experiment. In

general, the structures were solved with an incomplete

data set (50% or less completeness) while the measure-

ment was still executing, because the correct chemical

formula cannot always be predicted when solvent mole-

cules co-crystallize with the complex (13a, 21 and 22).

The corrected formula was then used for the ﬁnal

Table 5

Crystallographic details of 1, 3 and 5

1

3

5

Formula

M_r(g mol^ꢀ1

Crystal system

C

647.6

₂₆H₄₅O₆P₃Ru

C₁₈H₂₉O₆P₃Ru

535.39

C₂₆H₄₅FeO₆P₃

602.38

)

Monoclinic

P2₁/n

Orthorhombic

P2₁2₁2₁

Monoclinic

P2₁/n

Space group [No.]

˚

a (A)

˚

14.9483(9)

19.6736(14)

10.5705(6)

90, 92.508(7), 90

3105.7(3)

4

11.6423(8)

14.2702(8)

13.5705(9)

90, 90, 90

2254.6(2)

4

14.9087(7)

19.2328(12)

10.5482(5)

90, 91.292(6), 90

3023.8(3)

4

b (A)

˚

c (A)

a, b, c (ꢁ)

3

˚

V (A )

Z

Crystal dimensions (mm)

d(calcd) (g cm^ꢀ3

0.43 · 0.32 · 0.29

1.385

0.694

0.26 · 0.11 · 0.09

1.577

0.939

0.37 · 0.33 · 0.13

1.323

0.693

)

Absorption coeﬃcient, l (mm^ꢀ1

F(0 0 0)

)

1352

5.66 < 2h <60.54

1096

6.0 < 2h < 60.74

1280

5.74 < 2h < 60.72

2h scan range (ꢁ)

No. of measured ref.

No. of ref. I > 2r(I)

Unique data

34,297

6944

29,400

4869

33,723

4638

9168

0.8530–0.7932

333

6432

0.9195–0.8187

257

8319

0.9206–0.8188

333

Transmission range

No. of parameters

R₁, wR₂(%) all data

R₁, wR₂(obsd) (%)^a

Goodness-of-ﬁt

5.02, 10.57

3.66, 10.19

1.001

9.08, 19.72

7.41, 18.82

1.246

6.91, 5.12

3.05, 4.72

0.889

P

2

2 1=2

a

R₁

¼

ðF _oꢀ F _cÞ= F _o; I > rðIÞ; wR₂¼ f wðF ²_oꢀ F _c²Þ = wðF _o²Þ g

.

Table 6

Crystallographic details of 13a, 21 and 22

13a

21

22

Formula

M_r(g mol^ꢀ1

crystal system

C

₂₈H₅₀IO_6.25P₃Ru

C₄₄H₆₀BCl₂FeO₆P₃

915.39

C₂₈H₄₉Cl₄I₂O₆P₃Ru

1071.25

)

807.56

Triclinic

Monoclinic

P2₁/n

monoclinic

P2₁/c

ꢀ

Space group [No.]

˚

P1

a (A)

˚

13.4296(7)

15.2303(9)

20.7337(15)

17.8454(13)

11.3696(6)

22.7120(18)

90, 98.367(9), 90

4559.1(5)

11.5653(8)

13.7235(5)

28.1248(16)

90, 100.302(7), 90

4391.9(4)

b (A)

˚

c (A)

a, b, c (ꢁ)

74.829(8), 71.419(8), 67.619(7)

3669.0(4)

3

˚

V (A )

Z

4

Crystal dimensions (mm)

d(calcd) (g cm^ꢀ3

0.16 · 0.10 · 0.07

1.462

1.434

0.37 · 0.21 · 0.10

1.334

0.598

0.37 · 0.22 · 0.06

1.620

2.148

)

Absorption coeﬃcient, l (mm^ꢀ1

F(0 0 0)

)

1640

4.4 < 2h < 56.12

1928

5.1 < 2h < 60.66

2112

5.06 < 2h < 55.92

2h scan range (ꢁ)

No. of measured ref.

No. of ref. I > 2r(I)

Unique data

39,215

3363

49,145

5149

34,289

4932

16,330

0.9222–0.8797

723

13,263

0.9447–0.8519

520

10,409

0.7967–0.5707

383

Transmission range

No. of parameters

R₁, wR₂(%) all data

R₁, wR₂(obsd) (%)^a

Goodness-of-ﬁt

22.40, 17.85

4.22, 9.14

0.422

13.64, 13.87

5.44, 12.08

0.715

10.74, 14.34

5.16, 12.75

0.799

P

2

2 1=2

a

R₁¼ ðF _oꢀ F _cÞ= F _o; I > rIÞ; wR₂¼ f wðF ²_oꢀ F _c²Þ = wðF _o²Þ g

:

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1445

absorption corrections. All measurement procedures

were calculated by using the Stoe IPDS software [77].

The measurement temperatures were controlled by an

Oxford cryogenic system. The absolute structure of 3

(non-centrosymmetric space group P2₁2₁2₁) was con-

ﬁrmed by reﬁning the Flack parameter to ꢀ0.13(7)

[79]. It should be noted that for compounds 13a, 21

and 22 only about 20%, 39% and 47% of the unique

reﬂections were observed by criterion I > 2r(I). This cor-

responds to the low goodness-of-ﬁt values for these

structures (Table of crystallographic details).

The structures were solved with the merged data sets

after checking for correct space groups. The Patterson

or direct methods were used to solve the crystal struc-

tures by applying the software options of the program

SHELXS-97 [80]. The structure reﬁnements were per-

formed with the program ^SHELXL-97 [81]. The programs

PLATON and PLUTON [82] were used to check the results

of the X-ray analyses, they were also used for the com-

pletion of the structures by checking the diﬀerence elec-

tron density calculations. Relevant crystallographic data

are collected in Tables 5 and 6.

(Fax: + 44-1223-336033 or email: deposit@ccdc.cam.

ac.uk or http://www.ccd.cam.ac.uk).

12. Experimental

All manipulations of air-sensitive compounds were

carried out either in a dry glove-box under recirculating

nitrogen or under dry nitrogen by conventional Schlenk

techniques. Solvents were distilled from appropriate

drying agents and freshly distilled under nitrogen prior

to use (e.g., pentane, benzene, and toluene were puriﬁed

by reﬂuxing over sodium/benzophenone, dichlorome-

thane was reﬂuxed either over calcium hydride or

P₂O₅). The deuterated solvents (C₆D₆, CD₂Cl₂) were ob-

tained from commercial suppliers and distilled from

appropriate drying agents and vacuum transferred for

storage in Schlenk ﬂasks ﬁtted with Teﬂon stopcocks.

¹H, ³¹P and ¹³C NMR spectra were run on a Varian

Gemini-2000 spectrometer operating at 300.1, 121.5

and 75.4 MHz, respectively (d(¹H), d(¹³C) rel. to SiMe₄,

d(³¹P) rel. to 85% H₃PO₄). IR spectra were recorded on

a Bio-Rad FTS-45 instrument. Elemental analyses were

measured on a LECO CHNS-932 instrument. The irra-

diation experiments were carried out with a Philips HPK

125 high-pressure mercury lamp, cooled with a double-

walled borosilicate water jacket.

10. Conclusion

The ruthenium dicarbonyl complexes (1–4) undergo

fast oxidative addition reactions with MeI while the re-

lated iron complexes (5–8) react much slower. The oxi-

dative addition of EtI, n-PrI or i-PrI to 1–8 did not

produce the expected alkyl metal complexes. Instead

the iodo complexes 22–29 were obtained. The iron-ace-

tyl complexes (34–37) proved to be much more acidic

than the related ruthenium-acetyl complexes (30–33).

In all the deprotonation experiments, we were unable

to observe any ketene–metal intermediate. Exemplary

investigations with labelled (²H and ¹³C) acetyl com-

plexes (38 and 39) were also performed. It was clearly

established that deprotonation of the acetyl group oc-

curs, but evidence for ketene–metal complexes or free

ketene could not be obtained. On the basis of NMR

studies, it is assumed that the ketene-complexes are

not stable and that the released ketene reacts with the

base added to non-identiﬁable, presumably polymeric

compounds, as it was observed in an independent exper-

iment involving the addition of free ketene to BEMP.

The diﬀerent transition metal carbonyl compounds

Fe(CO)₅(Alfa products), Ru₃(CO)₁₂(Aldrich or Acros)

and Fe(COT)(CO)₃(Aldrich) were commercial products

and used as received, MePCl₂was graciously provided

by Hoechst Knapsack, DBU and BEMP were pur-

chased from Fluka. The alkyl iodides were purchased

from Aldrich and distilled prior to use. CD₃I and

¹³CH₃I were used as received from commercial suppliers

(Aldrich or Fluka). Phenylphosphine and cyclohexyl-

phosphine were commercially available (Strem).

Diisopropylallylphosphonite and dimethylallylphospho-

nite were prepared following a literature procedure [34].

12.1. General procedure to obtain I–IV

A 20-mL schlenk was charged with 1 eq. of the re-

quired primary phosphine, 2 eq. of di-alkylallylphosph-

onite and 50 mg of AIBN. The mixture was irradiated

from the outside for 48 h at room temperature with con-

stant stirring. The ligands were obtained in quantitative

yields as colourless viscous liquids suﬃciently pure to be

used directly without further puriﬁcation.

11. Supporting material

Crystallographic data for structures 1, 3, 5, 13a, 21

and 22 have been deposited with the Cambridge Crystal-

lographic Data Center, CCDC No. 250413, 250414,

250415, 250416, 250417 and 250418. Copies of the data

can be obtained, free of charge, on application to

CCDC, 12 Union road, Cambridge CB2 1EZ, UK

12.1.1. PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂(I)

1.16 g (10.5 mmol) of phenylphosphine and 4 g

(21 mmol) of diisopropylallylphosphonite. Anal. Calc.

for C₂₄H₄₅O₄P₃(490.6): C, 58.76%; H, 9.25%. Found:

C, 58.90%; H, 9.50%. ¹H NMR (CD₂Cl₂, 298 K):

1.1 (d, ³J_HH= 6 Hz, –CH(CH₃)₂), 1.6–1.8 (m,

1446

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

–CH₂CH₂CH₂–), 4–4.2 (m, –CH(CH₃)₂), 7–7.6 (m,

–P(C₆H₅)). ³¹P{¹H} NMR (CD₂Cl₂, 298 K): ꢀ25.7

(s, –P(C₆H₅)), 179.9 (s, –P[OCH(CH₃)₂]₂). ¹³C{¹H}

16.9 Hz, –CH₂CH₂CH₂–), 25.9 (dd, J_CP= 16.2 Hz,

J_CP= 10.4 Hz, –CH₂CH₂CH₂–P(C₆H₁₁)), 26.6 (s, cyclo-

2

hexyl C para), 27.2 (d, J_CP= 9.6 Hz, cyclohexyl

2

3

C meta), 29.4 (d, J_CP= 11.8 Hz, cyclohexyl C ortho),

NMR (CD₂Cl₂, 298 K): 19.5 (ꢁtꢀ, J_CP= 16 Hz,

1

35.2 (d, J_CP= 12.6 Hz, cyclohexyl

–CH₂CH₂CH₂–), 24.6 (s, –CH(CH₃)₂), 30 (ꢁtꢀ, J_CP

=

C

(dd, J_CP= 19.3 Hz, J_CP= 10.2 Hz, –CH₂CH₂CH₂–

ipso), 35.3

3

11 Hz, J_CP= 11 Hz, –H₂CH₂CH₂–P(C₆H₅)), 37.3 (ꢁtꢀ,

¹J_CP= 11 Hz, J_CP= 11 Hz, –CH₂CH₂CH₂–P[OCH-

3

2

P(OCH₃)₂), 53.3 (d, J_CP= 11.2 Hz, –P(OCH₃)₂).

2

(CH₃)₂]₂), 70.6 (d, J_CP= 29 Hz, –P[OCH(CH₃)₂]₂),

3

(Phenyl: 128.5 (d, J_CP= 7 Hz, C meta), 128.7 (s, C

12.2. General procedure for the preparation of the

ruthenium dicarbonyl complexes 1–4

2

1

para), 132.8 (d, J_CP= 17 Hz, C ortho), 139.6 (d, J_CP

19 Hz, C ipso)).

=

The required tridentate phosphine ligand (I–IV) was

added to a suspension of Ru₃(CO)₁₂(1/3 eq.) in dry tolu-

ene. Slow CO evolution was observed and the mixture

was heated to 40 ꢁC during 4 h during which time the

CO evolution stopped and all the Ru₃(CO)₁₂had dis-

solved. The mixture was then heated to reﬂux for a period

of 4 days during which time the colour changed from dark

red to light yellow and all the free ligand was consumed,

as observed by ³¹P NMR monitoring. The toluene was

then removed under vacuum to give a yellow solid. This

residue was extracted with pentane. The pentane extracts

were ﬁltered over Celite using a frit. Recrystallisation in

cold (ꢀ30 ꢁC) toluene aﬀorded the air-sensitive ruthe-

nium dicarbonyl complexes as light yellow solids.

12.1.2. CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂(II)

917 mg (7.9 mmol) of cyclohexylphosphine and 3 g

(15.8 mmol) of diisopropylallylphosphonite. Anal. Calc.

for C₂₄H₅₁O₄P₃(496.6): C, 58.00%; H, 10.36%. Found:

C, 57.85%; H, 10.15%. ¹H NMR (CD₂Cl₂, 298 K):

1.2 (d, ³J_HH= 6 Hz, –CH(CH₃)₂), 1.6–1.9 (m,

–CH₂CH₂CH₂– and –P(C₆H₁₁)), 4–4.2 (m, –CH(CH₃)₂).

³¹P{¹H} NMR (CD₂Cl₂, 298 K): ꢀ19.5 (s, –P(C₆H₁₁)),

183.3 (s, –P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR (CD₂Cl₂,

2

298 K): 19.9 (ꢁtꢀ, J_CP= 16.4 Hz, –CH₂CH₂CH₂–), 24.6

1

3

(s, –CH(CH₃)₂), 26 (ꢁtꢀ, J_CP= 11 Hz, J_CP= 11 Hz,

–CH₂CH₂CH₂–P(C₆H₁₁)), 26.7 (s, cyclohexyl C para),

3

27.2 (d, J_CP= 9 Hz, cyclohexyl C meta), 29.4 (d,

²J_CP= 12 Hz, cyclohexyl C ortho), 35.2 (d, ¹J_CP= 12 Hz,

1

3

cyclohexyl C ipso), 37.5 (ꢁtꢀ, J_CP= 10 Hz, J_CP

10 Hz, –CH₂CH₂CH₂–P[OCH(CH₃)₂]₂), 70.7 (d,

=

12.2.1. Ru(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)(CO)₂(1)

980 mg (2 mmol) of I and 430 mg (0.7 mmol of Ru) of

Ru₃(CO)₁₂in 20 mL of toluene. Recrystallisation from

toluene/pentane at ꢀ30 ꢁC gave 970 mg (1.5 mmol,

75%) of 1 as a light yellow powder. Suitable crystals

for X-ray diﬀraction were obtained from a cold

(ꢀ30 ꢁC) toluene solution. Anal. Calc. for C₂₆H₄₅O₆-

P₃Ru (647.6): C, 48.22%; H, 7.00%. Found: C,

²J_CP= 23 Hz, –P[OCH(CH₃)₂]₂).

12.1.3. PhP[CH₂CH₂CH₂P(OMe)₂]₂(III)

990 mg (9 mmol) of phenylphosphine and 2.5 g

(18 mmol) of dimethylallylphosphonite. Anal. Calc. for

C₁₆H₂₉O₄P₃(378.3): C, 50.80%; H, 7.73%. Found: C,

51.20%; H, 7.78%. ¹H NMR (CD₂Cl₂, 298 K): 1.55–

1

48.60%; H, 7.21%. H NMR (CD₂Cl₂, 298 K): 0.8–2.4

3

1.80 (m, –CH₂CH₂CH₂–), 3.31 (d, J_HP= 11 Hz,

(m, –CH₂CH₂CH₂–), 0.92, 1.14, 1.4 and 1.45 (d,

³J_HH= 6 Hz, –P[OCH(CH₃)₂]₂), 4.58 and 5.49 (sept.,

³J_HH= 6 Hz, –P[OCH(CH₃)₂]₂), 6.9–8 (m, –P(C₆H₅)).

–P(OCH₃)₂), 7–7.55 (m, –P(C₆H₅)). ³¹P{¹H} NMR

(CD₂Cl₂, 298 K): ꢀ26.3 (s, –P(C₆H₅)), 189.8 (s,

–P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K): 19.5 (ꢁtꢀ,

²J_CP= 16 Hz, –CH₂CH₂CH₂–), 29.9 (dd, J_CP= 13 Hz,

J_CP= 10.6 Hz, –CH₂CH₂CH₂–P(C₆H₅)), 35.2 (dd,

2

³¹P{¹H} NMR (CD₂Cl₂, 298 K): 5.1 (t, J_PP= 54 Hz,

2

–P(C₆H₅)), 190.4 (d, J_PP= 54 Hz, –P[OCH(CH₃)₂]₂).

¹³C{¹H} NMR (CD₂Cl₂, 298 K): 19.1 (m, –CH₂-

CH₂CH₂–), 24.3 (m, –CH(CH₃)₂), 32.5 (dt, J_CP= 4.7,

24 Hz, –CH₂CH₂CH₂–P(C₆H₅)), 37.1 (dt, J_CP= 3.7,

24.7 Hz, –CH₂CH₂CH₂-P[OCH(CH₃)₂]₂), 68.9 (m,

–P[OCH(CH₃)₂]₂), (Phenyl: 127.8 (s, C para), 128.5 (d,

J_CP= 19.5 Hz,

J_CP= 10.6 Hz,

2

–CH₂CH₂CH₂–

P(OCH₃)₂), 53.3 (d, J_CP= 11.2 Hz, –P(OCH₃)₂), (Phe-

3

nyl: 128.6 (d, J_CP= 7.2 Hz, C meta), 128.9 (s, C para),

132.8 (d, ²J_CP= 16.9 Hz,

¹J_CP= 19.2 Hz, C ipso)).

C

ortho), 139.3 (d,

2

³J_CP= 7 Hz, C meta), 133.6 (d, J_CP= 16 Hz, C ortho),

1

138.3 (d, J_CP= 22 Hz, C ipso)), 211 and 218 (m, CO).

12.1.4. CyP[CH₂CH₂CH₂P(OMe)₂]₂(IV)

IR (CD₂Cl₂, cm^ꢀ1): m_CO1851 (s) and 1912 (s).

2.1 g (18 mmol) of cyclohexylphosphine and 5 g

(36 mmol) of dimethylallylphosphonite. Anal. Calc. for

C₁₆H₃₅O₄P₃(384.3): C, 50.00%; H, 9.18%. Found: C,

50.13%; H, 9.48%. H NMR (CD₂Cl₂, 298 K): 1.1–1.8

(m, –CH₂CH₂CH₂– and –P(C₆H₁₁)), 3.37 (d,

³J_HP= 11 Hz, –P(OCH₃)₂). ³¹P{¹H} NMR (C₆H₆,

12.2.2. Ru(CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)(CO)₂(2)

990 mg (2 mmol) of II and 430 mg (0.7 mmol) of

Ru₃(CO)₁₂in 20 mL of toluene. Recrystallisation from

toluene/pentane at ꢀ30 ꢁC gave 880 mg (1.35 mmol,

67%) of 2 as a light yellow powder. Anal. Calc. for

C₂₆H₅₁O₆P₃Ru (653.6): C, 47.77%; H, 7.86%. Found:

C, 47.80%; H, 7.53%. ¹H NMR (CD₂Cl₂, 298 K):

1

298 K): ꢀ20.1 (s, –P(C₆H₅)), 190.2 (s, –P(OCH₃)₂).

2

¹³C{¹H} NMR (CD₂Cl₂, 298 K): 19.5 (ꢁtꢀ, J_CP

=

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1447

0.8–2.4 (m, –PCH₂CH₂CH₂P–, –P[OCH(CH₃)₂]₂and

–P(C₆H₁₁)), 4.5 and 5.0 (sept., ³J_HP= 6 Hz,

–P[OCH(CH₃)₂]₂). ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

The vessel was evacuated and reﬁlled with CO three

times. Sodium naphtalide (3.5 mmol, prepared from

450 mg of naphthalene and an excess of sodium in

5 mL of THF) was then added under CO atmosphere,

the Schlenk was closed and the temperature was allowed

to warm up slowly to room temperature. The reaction

mixture was stirred overnight. Filtration over Celite^ꢂ

followed by removal of THF under vacuum gave a light

orange solid. The residue was extracted with pentane

and recrystallisation from toluene/pentane at ꢀ30 ꢁC

yielded 680 mg (1.1 mmol, 67%) of 5. Suitable crystal

for X-ray diﬀraction were obtained from a cold

(ꢀ30 ꢁC) saturated toluene solution. Anal. Calc. for

C₂₆H₄₅O₆P₃Fe (602.4): C, 51.84%; H, 7.53%. Found:

2

4.5 (t, J_PP= 51 Hz, –P(C₆H₁₁)), 192.2 (d, J_PP= 51 Hz,

–P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR (C₆D₆, 298 K): 20.1

(m, –CH₂CH₂CH₂–), 24.5 (m, –CH(CH₃)₂), 26.6 (dt,

J_CP= 4.3, 21 Hz, –CH₂CH₂CH₂–P(C₆H₁₁)), 27 (s,

Cyclohexyl C para), 28.1 (d, ³J_CP= 11.3 Hz, Cyclohexyl

2

C meta), 29.7 (d, J_CP= 12,1 Hz, Cyclohexyl C ortho),

–CH₂CH₂CH₂-

37.1

(dt,

J_CP= 4,

24.6 Hz,

1

P[OCH(CH₃)₂]₂), 38.4 (d, J_CP= 14 Hz, Cyclohexyl C

ipso), 69.2 (m, –P[OCH(CH₃)₂]₂), 215.4 (br, CO)). IR

(CD₂Cl₂, cm^ꢀ1): m_CO1842 (s) and 1901 (s).

1

12.2.3. Ru(PhP[CH₂CH₂CH₂P(OMe)₂]₂)(CO)₂(3)

980 mg (2.6 mmol) of III and 560 mg (0.9 mmol of

Ru) of Ru₃(CO)₁₂in 20 mL of toluene. Recrystallisation

from toluene/pentane at ꢀ30 ꢁC gave 940 mg (1.7 mmol,

67%) of 3 as a light yellow powder. Anal. Calcd. for

C₁₈H₂₉O₆P₃Ru (535.4): C, 40.38%; H, 5.46%. Found:

C, 51.52%; H, 7.51%. H NMR (CD₂Cl₂, 298 K): 0.8–

2.4 (m, –CH₂CH₂CH₂–), 0.85, 0.95, 1.06 and 1.48 (m,

3

–P[OCH(CH₃)₂]₂), 4.48 and 5.49 (sept., J_HP= 6 Hz,

–P[OCH(CH₃)₂]₂), 7–7.9 (m, –P(C₆H₅)). ³¹P{¹H}

NMR (CD₂Cl₂, 298 K): 25.6 (t, ²J_PP= 79 Hz,

2

–P(C₆H₅)), 215.1 (d, J_PP= 79 Hz, –P[OCH(CH₃)₂]₂).

1

C, 40.20%; H, 5.60%. H NMR (CD₂Cl₂, 298 K): 1.2–

2.4 (m, –CH₂CH₂CH₂–), 3.4 and 3.73 (m, –P(OCH₃)₂),

7.4–7.8 (m, –P(C₆H₅)). ³¹P{¹H} NMR (CD₂Cl₂,

¹³C{¹H}

NMR

(CD₂Cl₂, 298 K):

19.4

(m,

–CH₂CH₂CH₂–), 24.5 (m, –CH(CH₃)₂), 32.1 (dt,

J_CP= 26, 7 Hz, –CH₂CH₂CH₂–P(C₆H₅)), 37.1 (ꢁtꢀ,

J_CP= 22 Hz, –CH₂CH₂CH₂–P[OCH(CH₃)₂]₂), 68.7

2

298 K): 5.6 (t, J_PP= 56.4 Hz, –P(C₆H₅)), 197.5 (d,

²J_PP= 56.4 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

298 K): 18.8 (m, –CH₂CH₂CH₂–), 32.8 (dt, J_CP= 24.6,

4.8 Hz, –CH₂CH₂CH₂–P(C₆H₁₁)), 33.8 (dt, J_CP= 4.7,

23.8 Hz, –CH₂CH₂CH₂–P(OCH₃)₂), 51.9 and 52.7 (m,

and 69.6 (m, –P[OCH(CH₃)₂]₂), (Phenyl: 129.6 (s, C

3

para), 128 (d, J_CP= 9 Hz,

C meta), 133.5 (d,

1

²J_CP= 14 Hz, C ortho), 138.8 (d, J_CP= 27 Hz, C ipso),

217 and 221 (m, CO)). IR (C₆H₆, cm¹): m_CO1839 (s)

and 1895 (s).

3

–P(OCH₃)₂), (Phenyl: 128.2 (d, J_CP= 9.7 Hz, C meta),

2

129.9 (s, C para), 133.7 (d, J_CP= 16.3 Hz, C ortho),

1

137.8 (d, J_CP= 25 Hz, C ipso)), 215.5 (br m, CO)). IR

12.2.6. Fe(CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)(CO)₂(6)

The phosphine ligand II (1.6 g, 3.2 mmol) was slowly

added to a suspension of FeI₂(1 g, 3.2 mmol) in 25 mL

of THF. The red coloured mixture was stirred overnight

at room temperature. The Schlenk was cooled to ꢀ78 ꢁC,

evacuated and reﬁlled with CO three times. A 10-ml THF

solution of sodium naphtalide (prepared from 900 mg

(7 mmol) of naphthalene and an excess of sodium) was

added to the mixture. The temperature was allowed to

warm up slowly to room temperature and the reaction

mixture was stirred overnight. Filtration over Celite^ꢂ

followed by removal of THF under vacuum gave a light

brown solid. The residue was extracted with pentane and

recrystallisation from toluene/pentane at ꢀ30 ꢁC aﬀor-

ded 1.2 g of 6 (1.9 mmol; 62%). Anal. Calc. for

C₂₆H₅₁O₆P₃Fe (608.4): C, 51.32%; H, 8.45%. Found:

(CD₂Cl₂, cm^ꢀ1): m_CO1856 (s) and 1911 (s).

12.2.4. Ru(CyP[CH₂CH₂CH₂P(OMe)₂]₂)(CO)₂(4)

990 mg (2.6 mmol) of IV and 560 mg (0.9 mmol of

Ru) of Ru₃(CO)₁₂in 20 mL of toluene. Recrystallisation

from toluene/pentane at ꢀ30 ꢁC gave 1 g (1.84 mmol,

71%) of 4 as a light yellow powder. Anal. Calc. for

C₁₈H₃₅O₆P₃Ru (541.4): C, 39.93%; H, 6.52%. Found:

1

C, 40.15%; H, 6.61%. H NMR (CD₂Cl₂, 298 K): 0.8–

2.2 (m, –CH₂CH₂CH₂– and –P(C₆H₁₁)), 3.52 and 3.69

(m, –P(OCH₃)₂). ³¹P{¹H} NMR (CD₂Cl₂, 298 K): 4.9

2

(t, J_PP= 55.8 Hz, –P(C₆H₁₁)), 201.6 (d, J_PP= 55.8 Hz,

–P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K): 19.7

(m, –CH₂CH₂CH₂–), 26.2 (dt, J_CP= 26.2, 5.2 Hz,

–CH₂CH₂CH₂–P(C₆H₁₁)), 26.9 (s, cyclohexyl C para),

3

1

28.1 (d, J_CP= 11.2 Hz, cyclohexyl C meta), 28.6

C, 51.12%; H, 8.22%. H NMR (CD₂Cl₂, 298 K): 0.9–

2.2 (m, –PCH₂CH₂CH₂P– and –P(C₆H₁₁)), 1.18–1.51

2

(d, J_CP= 12.6 Hz, cyclohexyl C ortho), 33.8 (dt,

J_CP= 4.6, 25.1 Hz, –CH₂CH₂CH₂–P(OCH₃)₂), 38.6

3

(m, –P[OCH(CH₃)₂]₂), 4.5 and 5.5 (sept., J_HP= 6 Hz,

1

(d, J_CP= 16.4 Hz, cyclohexyl C ipso), 51.9 and 52.8

–P[OCH(CH₃)₂]₂). ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

25.1 (t, ²J_PP= 74.7 Hz, –P(C₆H₁₁)), 214.6 (d,

²J_PP= 74.7 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR

(C₆D₆, 298 K): 19.6 (m, –CH₂CH₂CH₂–), 24.6 (m,

2

(m, –P(OCH₃)₂), 215.8 (q, J_CP= 17.1 Hz, CO)). IR

(CD₂Cl₂, cm^ꢀ1): m_CO1848 (s) and 1903 (s).

12.2.5. Fe(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)(CO)₂(5)

In a Schlenk, 1.4 g (1.6 mmol) of 12 was dissolved in

25 mL of THF and the mixture was cooled to ꢀ78 ꢁC.

–CH(CH₃)₂),

25

(dt,

J_CP= 21.6,

6.7 Hz,

–CH₂CH₂CH₂–P(C₆H₁₁)), 27 (s, cyclohexyl C para), 28

3

(d, J_CP= 10.9 Hz, cyclohexyl

C meta), 29.8 (d,

1448

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

²J_CP= 12.5 Hz, cyclohexyl C ortho), 35.1 (dt, J_CP= 2.7,

20.7 Hz, –CH₂CH₂CH₂-P[OCH(CH₃)₂]₂), 37.9 (d,

¹J_CP= 18.5 Hz, Cyclohexyl C ipso), 67.5 (m, –P[OCH-

(CH₃)₂]₂), 218.1 (br, CO)). IR (C₆H₆, cm^ꢀ1): m_CO1828

(s), 1891 (s).

of toluene and heated to 80 ꢁC for 8 h. Recrystallisation

from a cold (ꢀ30 ꢁC) toluene/pentane mixture aﬀorded

194 mg (0.31 mmol, 77%) of the product. Anal. Calc.

for C₂₇H₄₅O₇P₃Fe (630.4): C, 51.44%; H, 7.19%. Found:

C, 51.47%; H, 7.19%. ³¹P{¹H} NMR (C₆D₆, 298 K):

2

35.2 (d, J_PP= 96.7 Hz, –P(C₆H₅)), 178.2 (s, uncoordi-

2

nated –P[OCH(CH₃)₂]₂), 205.4 (d, J_PP= 96.7 Hz, coor-

dinated –P[OCH(CH₃)₂]₂).

12.2.7. Fe(PhP[CH₂CH₂CH₂P(OMe)₂]₂)(CO)₂(7)

The phosphine ligand III (760 mg, 2 mmol) and

Fe(CO)₅(0.27 mL, 2 mmol) in 20 mL of benzene were

irradiated for 4–5 h after which time all free III was con-

sumed (³¹P NMR spectroscopy monitoring). The ben-

zene was removed under vacuum and the residue was

puriﬁed by column chromatography (benzene/THF).

Recrystallisation from toluene/pentane at ꢀ30 ꢁC aﬀor-

ded 351 mg (0.7 mmol, 36%) of 7. Anal. Calc. for

C₁₈H₂₉O₆P₃Fe (490.2): C, 44.10%; H, 5.96%. Found: C,

12.2.10. Fe(g²-PhP[CH₂CH₂CH₂P(OMe)₂]₂)(CO)₃

(10)

Fe(COT)(CO)₂(100 mg, 0.4 mmol) and the phos-

phine ligand III (150 mg, 0.4 mmol) were mixed in 2

mL of toluene and heated to 80 ꢁC for 8 hours. Recrys-

tallisation from a cold (ꢀ30 ꢁC) toluene/pentane mixture

aﬀorded 136 mg (0.26 mmol, 66%) of the product. Anal.

Calc. for C₁₉H₂₉O₇P₃Fe (518.2): C, 44.04%; H, 5.64%.

Found: C, 44.21%; H, 5.78%. ³¹P{¹H} NMR (C₆D₆,

1

44.27%; H, 6.35%. H NMR (CD₂Cl₂, 298 K): 1.5–2.2

(m, –PCH₂CH₂CH₂P–), 3.39 and 3.78 (m, –P(OCH₃)₂),

7.35–7.82 (m, –P(C₆H₅)). ³¹P{¹H} NMR (CD₂Cl₂,

2

298 K): 36.5 (d, J_PP= 97.1 Hz, –P(C₆H₅)), 182.7 (s,

2

298 K): 25.8 (t, J_PP= 82.2 Hz, –P(C₆H₅)), 222 (d,

2

uncoordinated –P(OCH₃)₂), 213 (d, J_PP= 97.1 Hz,

coordinated –P(OCH₃)₂).

²J_PP= 82.2 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

298 K): 19.7 (m, –CH₂CH₂CH₂–), 31–31.8 (m,

–CH₂CH₂CH₂–P(C₆H₅)

and

–CH₂CH₂CH₂–

12.2.11. FeCl₂(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂) (11)

FeCl₂Æ 4H₂O (400 mg, 2 mmol) was suspended in 20

mL of methanol. The phosphine ligand I (1 g, 2 mmol)

was slowly added to the suspension resulting in an

immediate dark blue colour. The mixture was stirred

overnight at room temperature. The methanol was re-

moved under vacuum, leaving a dark brown solid. The

residue was recrystallized from methanol/ether. Com-

plex 11 was obtained as a brown microcrystalline mate-

rial (1.1 g, 1.7 mmol; 88%). The compound was

paramagnetic and exhibited no ³¹P NMR resonance.

Anal. Calc. for C₂₄Cl₂H₄₅O₄P₃Fe (617.3): C, 46.69%;

H, 7.35%. Found: C, 46.83%; H, 7.14%.

P(OCH₃)₂), 50.6 and 51.3 (m, –P(OCH₃)₂), (Phenyl:

127.9 (d, ³J_CP= 8.6 Hz, C meta), 129.5 (s, C para), 133.1

(d, ²J_CP= 14.7 Hz, C ortho), 138.5 (d, ¹J_CP= 30.8 Hz, C

ipso). IR (C₆H₆, cm^ꢀ1): m_CO1837 (s), 1895 (s).

12.2.8. Fe(CyP[CH₂CH₂CH₂P(OMe)₂]₂)(CO)₂(8)

The phosphine ligand IV (1 g, 2.6 mmol) and

Fe(CO)₅(0.35 mL, 2.6 mmol) in 25 mL of benzene were

irradiated from the outside for 5 h at room temperature

with constant stirring. The benzene was removed under

vacuum and the residue was puriﬁed by column chroma-

tography (benzene/THF). Recrystallisation from tolu-

ene/pentane at ꢀ30 ꢁC aﬀorded 360 mg of 8 (0.68

mmol; 28%). Anal. Calcd. for C₁₈H₃₅O₆P₃Fe (496.2):

C, 43.57%; H, 7.11%. Found: C, 43.21%; H, 7.16%.

¹H NMR (CD₂Cl₂, 298 K): 1.1–2.2 (m, –PCH₂-

CH₂CH₂P– and –P(C₆H₁₁)), 3.62 and 3.87 (m,

–P(OCH₃)₂). ³¹P{¹H} NMR (CD₂Cl₂, 298 K): 24.7 (t,

12.2.12. FeI₂(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂) (12)

The phosphine ligand I (1.6 g, 3.2 mmol) was slowly

added to a suspension of FeI₂(1 g, 3.2 mmol) in

40 mL of THF. The red coloured mixture was stirred

overnight at room temperature. THF was removed un-

der vacuum to leave a red-brown solid. The residue

was recrystallized from THF/pentane and washed with

pentane. Complex 12 was obtained as a red-brown

microcrystalline material (2.3 g, 2.9 mmol; 92%). The

compound was paramagnetic and exhibited no ³¹P

NMR resonance. Anal. Calc. for C₂₄H₄₅I₂O₄P₃Fe

(800.2): C, 36.02%; H, 5.67%. Found: C, 36.16%; H,

5.53%.

²J_PP= 82.2 Hz, –P(C₆H₁₁)), 222.8 (d, J_PP= 82.4 Hz,

2

–P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K): 19.4

(m, –CH₂CH₂CH₂–), 25.6 (dt, J_CP= 22.9, 7.3 Hz,

–CH₂CH₂CH₂–P(C₆H₁₁)), 27 (s, cyclohexyl C para),

3

28.2 (d, J_CP= 12 Hz, cyclohexyl C meta), 29.3 (d,

ortho), 35.1 (dt,

²J_CP= 10.2 Hz, cyclohexyl

J_CP= 3.2, 21.5 Hz, -CH₂CH₂CH₂–P(OCH₃)₂), 38.7 (d,

C

¹J_CP= 19.3 Hz, cyclohexyl

C

ipso), 51.8 (m,

–P(OCH₃)₂), 216.5 (br, CO)). IR (C₆H₆, cm^ꢀ1): m_CO

1826 (s), 1888 (s).

12.3. General procedure for the oxidative addition

reaction of MeI to 1–8

12.2.9. Fe(g²-PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)(CO)₃

(9)

Fe(COT)(CO)₂(100 mg, 0.4 mmol) and the phos-

phine ligand I (200 mg, 0.4 mmol) were mixed in 2 mL

The metal dicarbonyl complex (1–8, 0.5 mmol) in

2 mL of CH₂Cl₂was treated with an excess of MeI

(5 mmol) at room temperature and the reaction was

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1449

2

(d, J_CP= 12,2 Hz, cyclohexyl C ortho), 33.3 (dt,

J_CP= 4, 17.5 Hz, –CH₂CH₂CH₂–P[OCH(CH₃)₂]₂), 38.7

monitored by ³¹P NMR spectroscopy. The excess MeI

and CH₂Cl₂was removed under vacuum. The residue

was washed with pentane and recrystallized from

CH₂Cl₂/pentane.

1

(d, J_CP= 23.7 Hz, cyclohexyl

C ipso), 72.2 (m,

–P[OCH(CH₃)₂]₂), 199.3 (q, J_CP= 8 Hz, CO) and 201

2

(q, J_CP= 8 Hz, CO). IR (CD₂Cl₂, cm^ꢀ1): m_CO1997

12.3.1. mer,trans-[Ru(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂Me]I (13a) and mer,cis- [Ru(PhP[CH₂CH₂-

CH₂P(Oi-Pr)₂]₂)(CO)₂Me]I (13b)

(s). (14b) (selected data): ¹H NMR (CD₂Cl₂, 298 K):

3

ꢀ0.41 (q, J_HP= 7.6 Hz, Ru–CH₃). ³¹P{¹H} NMR

2

(CD₂Cl₂, 298 K): ꢀ0.5 (t, J_PP= 50 Hz, –P(C₆H₁₁)),

2

Treatment of 330 mg (0.5 mmol) of 1 with MeI

(0.15 mL, 2.5 mmol) gave 360 mg (0.46 mmol; 92%)

of 13a and 13b as an isomeric mixture which could

not be separated. Anal. Calc. for C₂₇H₄₈O₆P₃RuI

(789.6): C, 41.07%; H, 6.13%. Found: C, 41.28%; H,

6.26 %. (13a): ¹H NMR (CD₂Cl₂, 298 K): 0.17 (dt,

158.1 (d, J_PP= 50 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H}

2

NMR (CD₂Cl₂, 298 K): ꢀ17.1 (q, J_CP= 10.2 Hz, Ru–

CH₃). IR (CD₂Cl₂, cm^ꢀ1): m_CO2017 (s) and 2066 (s).

12.3.3. mer,trans-[Ru(PhP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂Me]I (15a) and mer,cis-[Ru(PhP[CH₂CH₂CH₂-

P(OMe)₂]₂)(CO)₂Me]I (15b)

3

³J_HP= 3 Hz (trans), J_HP= 5 Hz (cis), Ru–CH₃), 1–2.8

(m, –CH₂CH₂CH₂–), 1.18–1.33 (m, –P[OCH(CH₃)₂]₂),

3

4.42 and 5.53 (sept., J_HP= 6 Hz, –P[OCH(CH₃)₂]₂),

Treatment of 270 mg (0.5 mmol) of 3 with MeI (0.15

mL, 2.5 mmol) gave 290 mg (0.43 mmol, 86%) of 15a

and 15b as an isomeric mixture which could not be sep-

arated. Anal. Calc. for C₁₉H₃₂O₆P₃RuI (677.4): C,

33.69%; H, 4.76%. Found: C, 33.46%; H, 4.73%. (15a):

7.4–7.9 (m, –P(C₆H₅)). ³¹P{¹H} NMR (CD₂Cl₂,

2

298 K): ꢀ4.5 (t, J_PP= 33.6 Hz, –P(C₆H₅)), 155.7 (d,

²J_PP= 33.6 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR

2

(CD₂Cl₂, 298 K): ꢀ22.8 (dt, J_CP= 25 Hz (trans),

3

¹H NMR (CD₂Cl₂, 298 K): 0.24 (dt, J_HP= 2.8 Hz

²J_CP= 6.6 Hz (cis), 24.3 (m, –CH(CH₃)₂), 24.5

(m, –CH₂CH₂CH₂–), 30.5 (dt, J_CP= 29, 2.1 Hz,

–CH₂CH₂CH₂–P(C₆H₅)), 34.1 (dt, J_CP= 3.7, 17.3 Hz,

–CH₂CH₂CH₂P[OCH(CH₃)₂]₂), 72.4 (m, –P[OCH

3

(trans), J_HP= 5 Hz (cis), Ru–CH₃), 1.4–2.6 (m,

–CH₂CH₂CH₂–), 3.61 and 3.69 (m, –P(OCH₃)₂)), 7.2–

7.8 (m, –P(C₆H₅)). ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

ꢀ4.7 (t, ²J_PP= 34.7 Hz, –P(C₆H₅)), 167.1 (d,

²J_PP= 34.7 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

(CH₃)₂]₂). (Phenyl: 128.4 (s,

³J_CP= 9.8 Hz, C meta), 131.6 (d, J_CP= 13.1 Hz, C

C para), 129.5 (d,

2

298 K): ꢀ26.5 (dt, J_CP= 23.7 Hz (trans), J_CP= 6.8 Hz

(cis), Ru–CH₃), 18.3 (m, –CH₂CH₂CH₂–), 25.0 (dt,

J_CP= 25.7, 2.7 Hz, –CH₂CH₂CH₂–P(C₆H₁₁)), 31.1 (dt,

J_CP= 3.4, 19.7 Hz, –CH₂CH₂CH₂–P(OCH₃)₂), 54 (m,

–P(OCH₃)₂), (Phenyl: 125.8 (s, C para), 128.1 (d,

1

ortho), 133.8 (d, J_CP= 21 Hz, C ipso), 199 (dt,

2

²J_CP= 7.6, 15 Hz, CO) and 200.7 (dt, J_CP= 6.8,

16.8 Hz, CO). IR (CD₂Cl₂, cm^ꢀ1): m_CO2002 (s). (13b)

1

(selected data): H NMR (CD₂Cl₂, 298 K): ꢀ0.25 (q,

³J_HP= 7.8 Hz). ³¹P{¹H} NMR (CD₂Cl₂, 298 K): ꢀ2.7

2

³J_CP= 9.6 Hz, C meta), 129.5 (d, J_CP= 15.4 Hz, C

2

(t, J_PP= 51 Hz, –P(C₆H₅)), 156.3 (d, J_PP= 51 Hz,

1

ortho), 131 (d, J_CP= 19.3 Hz, C ipso), 199.3 (dt,

–P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K):

²Jcp = 6.8, 16.9 Hz, CO) and 199.5 (dt, ²Jcp = 7.5,

2

ꢀ18 (q, J_CP= 11 Hz, Ru–CH₃). IR (CD₂Cl₂, cm^ꢀ1

)

15.6 Hz, CO). IR (CD₂Cl₂, cm^ꢀ1): m_CO2012 (s). (15b)

1968 (s), 2063 (s).

1

(selected data): H NMR (CD₂Cl₂, 298 K): ꢀ0.21 (q,

³J_HP= 8 Hz, Ru–CH₃). ³¹P{¹H} NMR (CD₂Cl₂,

12.3.2. mer,trans-[Ru(CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂Me]I (14a) and mer,cis-[Ru(CyP[CH₂CH₂CH₂-

P(Oi-Pr)₂]₂)(CO)₂Me]I (14b)

2

298 K): ꢀ3.1 (t, J_PP= 51 Hz, –P(C₆H₅)), 171 (d,

²J_PP= 51 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

298 K): ꢀ19.2 (q, ²J_CP= 9.7 Hz, Ru–CH₃). IR (CD₂Cl₂,

cm^ꢀ1): 1982 (s), 2048 (s).

Treatment of 330 mg (0.5 mmol) of 2 with MeI (0.15

mL, 2.5 mmol) gave 350 mg (0.45 mmol; 89%) of a 14a

and 14b as an isomeric mixture which could not be sep-

arated. Anal. Calc. for C₂₇H₅₄O₆P₃RuI (795.6): C,

40.76%; H, 6.82%. Found: C, 40.77%; H, 6.43 %.

(14a): ¹H NMR (CD₂Cl₂, 298 K): 0.12 (dt,

12.3.4. mer,trans-[Ru(CyP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂Me]I (16a) and mer,cis-[Ru(CyP[CH₂CH₂CH₂-

P(OMe)₂]₂)(CO)₂Me]I (16b)

3

³J_HP= 2.8 Hz (trans), J_HP= 5.2 Hz (cis), Ru–CH₃),

Treatment of 270 mg (0.5 mmol) of 4 with MeI (0.15

mL, 2.5 mmol) gave 321 mg (0.47 mmol, 94%) of 16a

and 16b as an isomeric mixture which could not be sep-

arated. Anal. Calc. for C₁₉H₃₈O₆P₃RuI (683.4): C,

33.39%; H, 5.60%. Found: C, 33.52%; H, 5.73%. (16a):

0.8–2.4 (m, –PCH₂CH₂CH₂P–, –O–CH(CH₃)₂and

–P(C₆H₁₁)), 4.4–4.8 (m, –O–CH(CH₃)₂). ³¹P{¹H}

NMR (CD₂Cl₂, 298 K): ꢀ3 (t, ²J_PP= 32 Hz,

2

–P(C₆H₁₁)), 158 (d, J_PP= 32 Hz, –P[OCH(CH₃)₂]₂).

3

¹³C{¹H} NMR (CD₂Cl₂, 298 K): ꢀ23.9 (dt,

¹H NMR (CD₂Cl₂, 298 K): 0.05 (dt, J_HP= 2.8 Hz

2

3

(trans), J_HP= 5 Hz (cis), Ru–CH₃), 1.1–2.2 (m,

²J_CP= 24 Hz (trans), J_CP= 6.9 Hz (cis), Ru–CH₃),

19.1 (m, –CH₂CH₂CH₂–), 24.6 (m, –CH(CH₃)₂), 25.6

(m, –CH₂CH₂CH₂–P(C₆H₁₁)), 26.4 (s, cyclohexyl C

3

para), 27.4 (d, J_CP= 10.8 Hz, cyclohexyl C meta), 31.4

–CH₂CH₂CH₂– and –PC₆H₁₁), 3.5–3.7 (m, –P(OC-

H₃)₂), 7.5–7.8 (m, –P(C₆H₅)). ³¹P{¹H} NMR (CD₂Cl₂,

298 K): ꢀ2.8 (t, J_PP= 34 Hz, –P(C₆H₅)), 168.9 (d,

2

1450

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

²J_PP= 34 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

12.3.6. mer,trans-[Fe(CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂Me]I (18a) and mer,cis-[Fe(CyP[CH₂CH₂CH₂-

P(Oi-Pr)₂]₂)(CO)₂Me]I (18b)

2

298 K): ꢀ26.1 (dt, J_CP= 24.5 Hz (trans), J_CP= 6.9 Hz

(cis), Ru–CH₃), 17.5 (m, –CH₂CH₂CH₂–), 26.4 (s, cyclo-

3

hexyl C para), 27.8 (d, J_CP= 10.2 Hz, cyclohexyl C

Treatment of 300 mg (0.5 mmol) of 6 with MeI (0.15

mL, 2.5 mmol) gave 324 mg (0.42 mmol, 86%) of 18a

and 18b as an isomeric mixture which could not be sep-

arated. Anal. Calc. for C₂₇H₅₄O₆P₃FeI (750.3): C,

43.22%; H, 7.25%. Found: C, 43.58%; H, 7.10%. (18a):

2

meta), 28.7 (d, J_CP= 14 Hz, cyclohexyl C ortho), 30.1

(dt, J_CP= 29.4, 2.8 Hz, –CH₂CH₂CH₂–P(C₆H₁₁)), 31.7

(dt, J_CP= 3.8, 19.6 Hz, –CH₂CH₂CH₂–P(OCH₃)₂),

1

39.6 (d, J_CP= 23.2 Hz, cyclohexyl C ipso), 54 (m,

2

–P(OCH₃)₂), 198.7 (dt, J_CP= 7.8, 15.8 Hz, CO) and

3

¹H NMR (CD₂Cl₂, 298 K): 0.21 (t, J_HP= 5.4 Hz, Fe-

2

198.9 (dt, J_CP= 7.4, 16.9 Hz, CO). IR (CD₂Cl₂,

CH₃), 1.1–2.5 (m, –PCH₂CH₂CH₂P– and –P(C₆H₁₁)),

1.3 (m, –P[OCH(CH₃)₂]₂), 4.5 and 4.7 (sept.,

cm^ꢀ1): m_CO2006 (s). (16b) (selected data): ¹H NMR

3

(CD₂Cl₂, 298 K): ꢀ0.45 (q, J_HP= 7.4 Hz, Ru–CH₃),

³J_HP= 6 Hz,

–P[OCH(CH₃)₂]₂).

2

³¹P{¹H}

(CD₂Cl₂, 298 K): 17.7 (t, J_PP= 50.1 Hz, –P(C₆H₁₁)),

NMR

1.1–2.2 (m, –CH₂CH₂CH₂– and –PC₆H₁₁), 3.4–3.7 (m,

–P(OCH₃)₂), 7.5–7.8 (m, –P(C₆H₅)). ³¹P{¹H}

2

182.7 (d, J_PP= 50.1 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H}

2

NMR (CD₂Cl₂, 298 K): ꢀ2.1 (t, J_PP= 51.9 Hz,

NMR (CD₂Cl₂, 298 K): ꢀ12.7 (t, ²J_P= 14.6 Hz, Fe-

CH₃), 19 (m, –CH₂CH₂CH₂–), 24.4 (m, –CH(CH₃)₂),

25.3 (dt, J_CP= 16.3, 4.8 Hz, –CH₂CH₂CH₂–P(C₆H₁₁)),

2

–P(C₆H₅)), 171.8 (d, J_PP= 51.9 Hz, –P(OCH₃)₂).

¹³C{¹H} NMR (CD₂Cl₂, 298 K): ꢀ20.1 (q,

²J_CP= 10.1 Hz, Ru–CH₃). IR (CD₂Cl₂, cm^ꢀ1): m_CO

1996 (s) and 2041 (s).

3

26.4 (s, cyclohexyl C para), 27.5 (d, J_CP= 11.5 Hz,

2

cyclohexyl C meta), 28.8 (d, J_CP= 14 Hz, cyclohexyl

C ortho), 31.6 (dt, J_CP= 13.2, 2.1 Hz, –CH₂CH₂CH₂–

1

P[OCH(CH₃)₂]₂), 38.7 (d, J_CP= 23.5 Hz, cyclohexyl C

12.3.5. mer,trans-[Fe(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂Me]I (17a) and mer,cis-[Fe(PhP[CH₂CH₂CH₂-

P(Oi-Pr)₂]₂)(CO)₂Me]I (17b)

2

ipso), 72.6 (m, –P[OCH(CH₃)₂]₂), 211.8 (dt, J_CP= 13,

2

29.4 Hz, CO) and 214.1 (dt, J_CP= 10.4, 32.5 Hz, CO).

Treatment of 300 mg (0.5 mmol) of 5 with MeI

(0.15 mL, 2.5 mmol) for 48 hours gave 366 mg

(0.49 mmol, 99%) of 17a and 17b as an isomeric mix-

ture which could not be separated. Anal. Calc. for

C₂₇H₄₈O₆P₃FeI (744.3): C, 43.54%; H, 6.45%. Found:

IR (CD₂Cl₂, cm¹): m_CO1968 (s). (18b) (selected data):

¹H NMR (CD₂Cl₂, 298 K): ꢀ0.31 (q, J_HP= 9.1 Hz,

3

Fe-CH₃). ³¹P{¹H} NMR (CD₂Cl₂, 298 K): 14.4 (t,

²J_PP= 88.8 Hz, –P(C₆H₁₁)), 181.9 (d, J_PP= 88.8 Hz,

2

–P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K):

ꢀ11.64 (q, ²J_CP= 20.6 Hz, Fe-CH₃), 207 (dt,

²J_CP= 15.1, 19 Hz, CO trans to –P(C₆H₁₁)), 211.6 (q,

²J_CP= 32 Hz, CO cis to the three P atoms). IR (CD₂Cl₂,

cm¹): m_CO1997 (s) and 2046 (s).

1

C, 43.21%; H, 6.13%. (17a) (selected data): H NMR

3

(CD₂Cl₂, 298 K): 0.37 (t, J_HP= 4.8 Hz, Fe-CH₃).

2

³¹P{¹H} NMR (CD₂Cl₂, 298 K): 18 (t, J_PP= 52 Hz,

2

–P(C₆H₅)), 182 (d, J_PP= 52 Hz, –P[OCH(CH₃)₂]₂).

¹³C{¹H} NMR (CD₂Cl₂, 298 K): ꢀ11.67 (t,

²J_CP= 14.4 Hz, Fe-CH₃), 19.1 (m, –CH₂CH₂CH₂–),

27.1 (m, –CH(CH₃)₂) 29.9 (m, –CH₂CH₂CH₂–

P(C₆H₅)), 35.6 (m, –CH₂CH₂CH₂– P[OCH(CH₃)₂]₂),

68.9 and 72.6 (m, –P[OCH(CH₃)₂]₂), (Phenyl: 127.9–

133.8), 212.1 and 213.9 (br, CO). IR (CD₂Cl₂, cm¹):

12.3.7. mer,trans-[Fe(PhP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂Me]I (19a) and mer,cis-[Fe(PhP[CH₂CH₂CH₂-

P(OMe)₂]₂)(CO)₂Me]I (19b)

Treatment of 245 mg (0.5 mmol) of 7 with MeI (0.15

mL, 2.5 mmol) gave 300 mg (0.48 mmol, 96%) of 19a

and 19b as an isomeric mixture which could not be sep-

arated. Anal. Calc. for C₁₉H₃₂O₆P₃FeI (632): C,

36.10%; H, 5.10%. Found: C, 36.36%; H, 5.01%. (19a)

(selected data): ¹H NMR (CD₂Cl₂, 298 K): 0.37 (t,

³J_HP= 4.8 Hz, Fe-CH₃). ³¹P{¹H} NMR (CD₂Cl₂,

1

m_CO1970(s). (17b): H NMR (CD₂Cl₂, 298 K): ꢀ0.20

(q,

³J_HP= 8.8 Hz,

–P[OCH(CH₃)₂]₂), 1.8–2.4 (m, –PCH₂CH₂CH₂P–),

Fe-CH₃),

1.25–1.38

(m,

3

4.49 and 4.6 (sept., J_HP= 6 Hz, –P[OCH(CH₃)₂]₂),

7–7.9 (m, –P(C₆H₅)). ³¹P {¹H} NMR (CD₂Cl₂,

2

298 K): 14 (t, J_PP= 90 Hz, –P(C₆H₅)), 177.8 (d,

2

298 K): 18.8 (t, J_PP= 56 Hz, –P(C₆H₅)), 196.4 (d,

²J_PP= 56 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

298 K): ꢀ14.8 (t, ²J_CP= 14.1 Hz, Fe-CH₃). IR (CD₂Cl₂,

²J_PP= 90 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR

2

(CD₂Cl₂, 298 K): ꢀ11.98 (q, J_CP= 18.7 Hz, Fe-

1

CH₃), 18.1 (m, –CH₂CH₂CH₂–), 24.1 (dt, J_CP= 5.5,

29.1 Hz, –CH₂CH₂CH₂–P(C₆H₅)), 24.7 (m, –CH-

(CH₃)₂), 25.1 (ꢁtꢀ, J_CP= 13 Hz, –CH₂CH₂CH₂–

P[OCH(CH₃)₂]₂), 72.6 and 73.9 (m, –P[OCH(CH₃)₂]₂),

cm¹): m_CO1976(s). (19 b): H NMR (CD₂Cl₂, 298 K):

ꢀ0.04 (q, ³J_HP= 8.4 Hz, Fe-CH₃), 1.7–2.4 (m,

–PCH₂CH₂CH₂P–), 3.3–3.6 (m, –P(OCH₃)₂), 7.4–7.7

(m, –P(C₆H₅)). ³¹P{¹H} NMR (CD₂Cl₂, 298 K): 15.9

3

2

(Phenyl: 129.3 (s, C para), 131.5 (d, J_CP= 9 Hz, C

C ortho), 134.5 (d,

(t, J_PP= 86 Hz, –P(C₆H₅)), 196.4 (d, J_PP= 86 Hz,

–P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K): ꢀ11.7

2

meta), 134 (d, J_CP= 9 Hz,

¹J_CP= 39 Hz, C ipso), 207.9 (dt, J_CP= 16.6, 20 Hz,

2

(q, J_CP= 17.9 Hz, Fe-CH₃), 18.7 (m, –CH₂CH₂CH₂–),

2

CO trans to –P(C₆H₅)), 210.3 (q, J_CP= 31 Hz, CO

30.1

(m,

–CH₂CH₂CH₂–P(C₆H₅)),

35.4

(m,

cis to the three P atoms). IR (CD₂Cl₂, cm¹): m_CO

1994 (s) and 2044 (s).

–CH₂CH₂CH₂–P(OCH₃)₂), 52.9 and 54.1 (m,

–P(OCH₃)₂), (Phenyl: 128.7 (s, C para), 131.2 (d,

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1451

2

³J_CP= 9 Hz, C meta), 132 (d, J_CP= 9.6 Hz, C ortho),

(10 eq., 0.15 mL, 1.5 mmol) at room temperature for

four days, to yield the iodo complexes 22–29. The latter

were better prepared from the instantaneous reaction of

1–8 with a stoichiometric amount of iodine in dichlo-

romethane at room temperature. Pentane was added

to the reaction mixture. The precipitated material was

washed with pentane and recrystallized from CH₂Cl₂/

pentane or CH₂Cl₂/benzene.

1

133.2 (d, J_CP= 36.8 Hz, C ipso), 217 (br, CO). IR

(CD₂Cl₂, cm¹): m_CO1990 (s) and 2046(s).

12.3.8. mer,trans-[Fe(CyP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂Me]I (20a) and mer,cis-[Fe(CyP[CH₂CH₂CH₂-

P(OMe)₂]₂)(CO)₂Me]I (20b)

Treatment of 247 mg (0.5 mmol) of 8 with MeI (0.15

mL, 2.5 mmol) gave 280 mg (0.44 mmol, 89%) of 20a

and 20b as an isomeric mixture which could not be sep-

arated. Anal. Calc. for C₁₉H₃₈O₆P₃FeI (638.1): C,

35.76%; H, 6.00%. Found: C, 35.58%; H, 5.82%. (20a):

12.4.1. mer,cis-[Ru(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂I]I (22)

Complex 1 (100 mg, 0.15 mmol) was treated with one

equivalent of I₂(38 mg, 0.15 mmol). Recrystallisation

from CH₂Cl₂/pentane aﬀorded 120 mg (0.13 mmol,

88%) of 22 as a light yellow powder. Anal. Calc. for

C₂₆H₄₅I₂O₆P₃Ru (901.5): C, 34.64%; H, 5.03%. Found:

C, 34.96%; H, 5.17%. ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

ꢀ12.7 (t, ²J_PP= 48 Hz, –P(C₆H₅)), 143.5 (d,

²J_PP= 48 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR

(CD₂Cl_2,298 K): 20.1 (m, –CH₂CH₂CH₂–), 23.3 (m,

–CH(CH₃)₂), 27.7 (m, –CH₂CH₂CH₂–P(C₆H₅)),

37.9 (m, –CH₂CH₂CH₂–P[OCH(CH₃)₂]₂), 72.9 (m,

–P[OCH(CH₃)₂]₂). (Phenyl: 128 (s, C para), 129.1 (d,

³J_CP= 11 Hz, C meta), 132 (d, ²J_CP= 14.3 Hz, C ortho),

¹H NMR (CD₂Cl₂, 298 K): 0.23 (t, J_HP= 5.2 Hz, Fe-

3

CH₃), 1–2.2 (m, –CH₂CH₂CH₂– and –P(C₆H₁₁)), 3.6

and 3.8 (m, –P(OCH₃)₂). ³¹P{¹H} NMR (CD₂Cl₂,

2

298 K): 20 (t, J_PP= 55 Hz, –P(C₆H₁₁)), 198.3 (d,

²J_PP= 55 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

2

298 K): ꢀ15.1 (t, J_CP= 14 Hz, Fe-CH₃), 18.7 (m,

–CH₂CH₂CH₂–), 26 (m, CH₂CH₂CH₂–P(C₆H₁₁)), 27

(s, cyclohexyl C para), 27.7 (d, ³J_CP= 3.3 Hz, cyclohexyl

C meta), 29 (d, ²J_CP= 10.6 Hz, cyclohexyl C ortho), 32.5

1

(m, –CH₂CH₂CH₂–P(OCH₃)₂), 39 (d, J_CP= 26.4 Hz,

cyclohexyl C ipso), 52.8 and 54.1 (m,–P(OCH₃)₂), 207

and 209 (br, CO). IR (CD₂Cl₂, cm^ꢀ1): m_CO1972 (s).

(20b) (selected data): ¹H NMR (CD₂Cl₂, 298 K):

1

2

133.9 (d, J_CP= 18.1 Hz, C ipso), 187.2 (dt, J_P= 81.3,

2

12.4 Hz, CO trans to P) and 189.4 (q, J_P= 11 Hz, CO

ꢀ0.18 (q, J_HP= 8.5 Hz, Fe-CH₃). ³¹P{¹H} NMR

3

2

(CD₂Cl₂, 298 K): 16.8 (t, J_PP= 85.9 Hz, –P(C₆H₁₁)),

trans to I). IR (CD₂Cl₂, cm^ꢀ1): m_CO2033 (s), 2086 (s).

197.2 (d, J_PP= 85.9 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR

2

(CD₂Cl₂, 298 K): ꢀ11.7 (q, J_CP= 20.6 Hz, Fe-CH₃)

12.4.2. mer,cis-[Ru(CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂I]I (23)

19 (m, –CH₂CH₂CH₂–), 25.1 (m, CH₂CH₂CH₂–

P(C₆H₁₁)), 33 (m, –CH₂CH₂CH₂–P(OCH₃)₂), 51–54

(m,–P(OCH₃)₂), 211 (br, CO). IR (CD₂Cl₂, cm^ꢀ1): m_CO

1996 (s), 2039 (s).

Complex 2 (100 mg, 0.15 mmol) was treated with one

equivalent of I₂(38 mg, 0.15 mmol). Recrystallisation

from CH₂Cl₂/pentane aﬀorded 130 mg (0.14 mmol,

96%) of 23. Anal. Calcd. for C₂₆H₅₁I₂O₆P₃Ru (907.5):

C, 34.41%; H, 5.66%. Found: C, 34.48%; H, 5.52%.

³¹P{¹H} NMR (CD₂Cl₂, 298 K): ꢀ10.2 (t, ²J_PP= 48 Hz,

12.3.9. mer,trans-[Fe(CyP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂Me]BPh4 (21)

2

Treatment of 120 mg (0.25 mmol) of 8 with MeI (0.08

mL, 1.25 mmol) for 2 days. The solvent was removed

under vacuum to leave a light brown solid. A solution

of sodium tetraphenylborate (100 mg, 0.3 mmol) in

5 mL of methanol was added to the residue and the mix-

ture was stirred for 2 h. The light yellow precipitate was

ﬁltered oﬀ over a frit and washed with methanol and

dried under vacuum to give 21 (147 mg, 18 mmol,

71%). Suitable crystals for X-ray diﬀraction were ob-

tained from crystallisation in a dichloromethane/pen-

tane solution at room temperature. Anal. Calc. for

BC₄₃H₅₈O₆P₃Fe (830.5): C, 62.18%; H, 7.04%. Found:

C, 62.20%; H, 7.21%.

–P(C₆H₁₁)), 145.5 (d, J_PP= 48 Hz, –P[OCH(CH₃)₂]₂).

¹³C{¹H}

NMR

(CD₂Cl₂, 298 K):

19.4

(m,

–CH₂CH₂CH₂–), 24.6 (m, –CH(CH₃)₂), 26.1 (m,

–CH₂CH₂CH₂–P(C₆H₁₁)), 27.2 (s, cyclohexyl C para),

3

28.3 (d, J_CP= 3.5 Hz, cyclohexyl C meta), 29.9 (d,

²J_CP= 10.9 Hz, cyclohexyl

J_CP= 22.1, 5 Hz, –CH₂CH₂CH₂– P[OCH(CH₃)₂]₂),

C

ortho), 37.3 (dt,

1

38.2 (d, J_CP= 27.3 Hz, cyclohexyl C ipso), 74.1 (m,

–P[OCH(CH₃)₂]₂), 188.1 (dt, ²J_P= 80, 11.4 Hz, CO

2

trans to P) and 189.9 (q, J_P= 11.2 Hz, CO trans to I).

IR (CD₂Cl₂, cm^ꢀ1): m_CO2029 (s), 2084 (s).

12.4.3. mer,cis-[Ru(PhP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂I]I (24)

12.4. General procedure for the oxidative addition

reaction of EtI, n-PrI, i-PrI and iodine to 1–8

Complex 3 (80 mg, 0.15 mmol) was treated with one

equivalent of I₂(38 mg, 0.15 mmol). Recrystallisation

from CH₂Cl₂/benzene aﬀorded 110 mg (0.14 mmol,

93%) of 24 as a light yellow solid. Anal. Calc. for

C₁₈H₂₉I₂O₆P₃Ru (789.2): C, 27.39%; H, 3.70%. Found:

C, 27.76%; H, 3.65%. ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

The metal dicarbonyl complex (1–8, 0.15 mmol) in

1 mL of CH₂Cl₂was treated with an excess of alkyl io-

dide (EtI (10 eq., 0.12 mL, 1.5 mmol); n-PrI or i-PrI

1452

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

ꢀ13.4 (t, ²J_PP= 47.3 Hz, –P(C₆H₅)), 155.5 (d,

²J_PP= 47.3 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

298 K): 17.5 (m, –CH₂CH₂CH₂–), 24.3 (dt, J_CP= 3.8,

C, 36.22%; H, 5.96%. Found: C, 36.40%; H, 6.07%.

2

³¹P{¹H} NMR (CD₂Cl₂, 298 K): 6.9 (t, J_PP= 81.9 Hz,

–P(C₆H₁₁)), 169.9 (d, ²J_PP= 81.9 Hz, –P[OCH(CH₃)₂]₂).

¹³C{¹H} NMR (CD₂Cl₂, 298 K): 18.7 (m, –CH₂-

CH₂CH₂–), 24 (m, –CH(CH₃)₂), 26.6 (m, –CH₂-

34.6 Hz, –CH₂CH₂CH₂–P(C₆H₁₁)), 26.1 (ꢁtꢀ, J_CP

19.5 Hz, –CH₂CH₂CH₂-P[O(CH₃)]₂), 54.8 and 56.6

=

3

(m, –P(OCH₃)₂), (Phenyl: 130 (d, J_CP= 9.1 Hz, C

CH₂CH₂–P(C₆H₁₁), cyclohexyl C para obscured), 27.4

C

2

meta), 131.8 (d, J_CP= 10.3 Hz, C ortho), 132.4 (s, C

3

(d, J_CP= 12.1 Hz, cyclohexyl

meta), 29 (d,

1

para), 132.9 (d, J_CP= 34.1 Hz, C ipso)), 187.3 (dt,

²J_CP= 15.6 Hz, cyclohexyl C ortho), 32 (m, –CH₂CH₂-

²J_CP= 83.2, 12.5 Hz, CO trans to –P(C₆H₅)) and 188.9

CH₂–P[OCH(CH₃)₂]₂), 39.9 (d, J_CP= 19.3 Hz, cyclo-

1

2

(q, J_CP= 11.2 Hz, CO trans to I). IR (CD₂Cl₂, cm^ꢀ1):

hexyl C ipso), 74–76 (m, –P[OCH(CH₃)₂]₂), 206–209

(br, CO). IR (CD₂Cl₂, cm^ꢀ1): m_CO2016 (s) and m_CO

2064 (s).

m_CO2014 (s) and 2072 (s).

12.4.4. mer,cis-[Ru(CyP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂I]I (25)

12.4.7. mer,cis-[Fe(PhP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂I]I (28)

Complex 4 (81 mg, 0.15 mmol) was treated with one

equivalent of I₂(38 mg, 0.15 mmol). Recrystallisation

from CH₂Cl₂/benzene aﬀorded 95 mg (0.12 mmol,

81%) of 25 as a light yellow solid. Anal. Calc. for

C₁₈H₃₅I₂O₆P₃Ru (795.3): C, 27.18%; H, 4.44%. Found:

C, 27.15%; H, 4.20%. ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

ꢀ10.6 (t, ²J_PP= 45.8 Hz, –P(C₆H₅)), 156.7 (d,

²J_PP= 45.8 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂,

298 K): 18.6 (m, –CH₂CH₂CH₂–), 24.9 (m,

–CH₂CH₂CH₂–P(C₆H₁₁)), 26.9 (s, cyclohexyl C para),

Complex 7 (80 mg, 0.16 mmol) was treated with one

equivalent of I₂(40 mg, 0.16 mmol). Recrystallisation

from CH₂Cl₂/benzene aﬀorded 114 mg (0.15 mmol,

96%) of 28 as a light yellow solid. Anal. Calc. for

C₁₈H₂₉I₂O₆P₃Fe (744): C, 29.06%; H, 3.93%. Found:

C, 29.37%; H, 4.25%. ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

5 (t, ²J_PP= 82.8 Hz, –P(C₆H₅)), 183.2 (d, ²J_PP= 82.8 Hz,

–P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K): 19 (m,

–CH₂CH₂CH₂–), 28.8 (m, –CH₂CH₂CH₂–P(C₆H₅)),

34.1 (m, –CH₂CH₂CH₂–P(OCH₃)₂), 52 and 53.7 (m,

3

27.4 (d, J_CP= 14 Hz, cyclohexyl C meta), 29.1 (d,

²J_CP= 8.8 Hz, cyclohexyl

C

ortho), 29.7 (m,

–P(OCH₃)₂), (Phenyl: 127.3 (d, J_CP= 9.3 Hz, C ortho),

2

–CH₂CH₂CH₂–P(OCH₃)₂), 37.9 (d, ¹J_CP= 20 Hz, cyclo-

hexyl C ipso), 54–55.8 (m, –P(OCH₃)₂), 189 (br, CO). IR

(CH₂Cl₂, cm^ꢀ1): m_CO2024 (s) and 2084 (s).

130.6 (d, ³J_CP= 8.2 Hz, C meta), 132.3 (s, C para), 133.5

(d, ¹J_CP= 40.1 Hz, C ipso), 207.1 and 211.4 (br, CO). IR

(CH₂Cl₂, cm¹): m_CO2022 (s) and m_CO2065 (s).

12.4.5. mer,cis-[Fe(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂I]I (26)

12.4.8. mer,cis- [Fe(CyP[CH₂CH₂CH₂P-

(OMe)₂]₂)(CO)₂I]I (29)

Complex 5 (100 mg, 0.17 mmol) was treated with one

equivalent of I₂(43 mg, 0.17 mmol). Recrystallisation

from CH₂Cl₂/pentane aﬀorded 100 mg (0.12 mmol,

69%). Anal. Calcd. for C₂₆H₄₅I₂O₆P₃Fe (856.2): C,

36.47%; H, 5.30%. Found: C, 36.31%; H, 5.18%. mer,

cis-[FeLig3(CO)₂I]I (26): ³¹P{¹H} NMR (CD₂Cl₂,

Complex 8 (80 mg, 0.16 mmol) was treated with one

equivalent of I₂(40 mg, 0.16 mmol). Recrystallisation

from CH₂Cl₂/benzene aﬀorded 104 mg (0.14 mmol,

87%) of 29 as a light yellow solid. Anal. Calc. for

C₁₈H₃₅I₂O₆P₃Fe (750): C, 28.82%; H, 4.70%. Found:

C, 29.11%; H, 4.79%. ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

7.9 (t, J_PP= 82 Hz, –P(C₆H₁₁)), 184.1 (d, J_PP= 82 Hz,

–P(OCH₃)₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K): 18.1 (m,

–CH₂CH₂CH₂–), 25.2 (s, cyclohexyl C para), 27.6 (d,

2

298 K): 5.8 (t, J_PP= 85 Hz, –P(C₆H₅)), 172 (d,

²J_PP= 85 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR

(CD₂Cl₂, 298 K): 18.9 (m, –CH₂CH₂CH₂–), 24.3–25.1

(m, –CH(CH₃)₂and –CH₂CH₂CH₂–P(C₆H₅)), 29.1 (dt,

J_CP= 4.2, 16.3 Hz, –CH₂CH₂CH₂–P[OCH(CH₃)₂]₂),

74.2 and 76.8 (m, –P[OCH(CH₃)₂]₂), (Phenyl: 127.9 (d,

³J_CP= 9.4 Hz, cyclohexyl

C

meta), 28.4 (m,

2

CH₂CH₂CH₂–P(C₆H₁₁)), 32 (d, J_CP= 13.2 Hz, cyclo-

hexyl C ortho), 34.3 (m, –CH₂CH₂CH₂–P(OCH₃)₂), 39

1

(d, J_CP= 18.3 Hz, cyclohexyl C ipso), 52.6 and 54 (m,

3

²J_CP= 9.3 Hz, C ortho), 131.1 (d, J_CP= 7.9 Hz, C

1

meta), 132.1 (s, C para), 133.5 (d, J_CP= 41.9 Hz, C

–P(OCH₃)₂), 206.6 and 209 (br, CO). IR (CH₂Cl₂,

cm¹): m_CO1997 (s) and m_CO2046 (s).

2

ipso), 206 (dt, J_CP= 34.9, 26.3 Hz, Fe-CO trans to

2

-PPh) and 210.8 (q, J_CP= 21.6 Hz, Fe-CO). IR

(CD₂Cl₂, cm^ꢀ1): m_CO2024 (s) and m_CO2067 (s).

12.5. General procedure for the reaction of 13a/b–20a/b

with CO

12.4.6. mer,cis- [Fe(CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂I]I (27)

Complex 6 (100 mg, 0.16 mmol) was treated with one

equivalent of I₂(40 mg, 0.16 mmol). Recrystallisation

from CH₂Cl₂/pentane aﬀorded 121 mg (0.14 mmol,

88%) of 27. Anal. Calc. for C₂₆H₅₁I₂O₆P₃Fe (862.3):

The respective isomeric complexes 13a/b–20a/b were

dissolved in CD₂Cl₂and stirred under an atmosphere

of carbon monoxide at room temperature. The com-

pleteness of the reactions was monitored by H NMR

spectroscopy. Elemental analysis for 30–37 could not

1

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

1453

be obtained due to decarbonylation on attempted isola-

tion of the acetyl complexes.

¹J_CP= 20.9 Hz, C ipso), 198 (br, CO), 259.2 (br,

C(O)CH₃). IR (CD₂Cl₂, cm^ꢀ1): 1604 (m), 2003 (s).

12.5.1. mer,trans-[Ru(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂(COMe)]I (30)

A dichloromethane solution of 13a/13b (250 mg,

0.3 mmol) was stirred overnight under CO. H NMR

(CD₂Cl₂, 298 K): 0.8–2.8 (m, –CH₂CH₂CH₂–), 1.15

12.5.4. mer,trans-[Ru(CyP[CH₂CH₂CH₂P-

(OMe)₂]₂)(CO)₂(COMe)]I (33)

A dichloromethane solution of 16a/b (200 mg,

0.3 mmol) was stirred for 48 h. ¹H NMR (CD₂Cl₂,

298 K): 1.2–2.6 (m, –CH₂CH₂CH₂– and C₆H₁₁P–),

2.42 (s, –C(O)CH₃), 3.4–3.9 (m, –P(OCH₃)₂). ³¹P{¹H}

1

and 1.35 (m, –P[OCH(CH₃)₂]₂), 2.53 (s, C(O)CH₃),

3

4.48 and 4.64 (m, J_HP= 6 Hz, –P[OCH(CH₃)₂]₂), 7.3–

2

NMR (CD₂Cl₂, 298 K): ꢀ5.2 (t, J_PP= 51.7 Hz,

7.8 (m, –P(C₆H₅)). ³¹P{¹H} NMR (CD₂Cl₂, 298 K):

ꢀ10.7 (t, ²J_PP= 51 Hz, –P(C₆H₅)), 153.3 (d,

²J_PP= 51 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR

(CD₂Cl₂, 298 K): 17.8 (m, –CH₂CH₂CH₂–), 24 (m,

–CH(CH₃)₂), 29.9 (m, –CH₂CH₂CH₂–P(C₆H₅)),

33.5 (m, –CH₂CH₂CH₂-P[OCH(CH₃)₂]₂), 50.4 (s,

C(O)CH₃), 73 (m, –P[OCH(CH₃)₂]₂), (Phenyl: 129 (s,

2

–P(C₆H₁₁)), 169.1 (d, J_PP= 51.7 Hz, –P(OCH₃)₂).

¹³C{¹H}

–CH₂CH₂CH₂–), 26.1 (m, –CH₂CH₂CH₂–P(C₆H₁₁),

NMR

(CD₂Cl₂, 298 K):

18.3

(m,

3

cyclohexyl C para obscured), 27.4 (d, J_CP= 11 Hz,

2

cyclohexyl C meta), 28.7 (d, J_CP= 8.4 Hz, cyclohexyl

C ortho), 29.4 (m, –CH₂CH₂CH₂–P(OCH₃)₂), 39.3 (d,

¹J_CP= 24.7 Hz, cyclohexyl C ipso), 49.8 (s, C(O)CH₃),

54 (m, –P(OCH₃)₂), 196 (br, CO), 259 (br, C(O)CH₃).

IR (CD₂Cl₂, cm^ꢀ1): m_C@O1611 (m) and m_CO2002 (s).

3

C para), 129.8 (d, J_CP= 10.2 Hz, C meta), 130.9 (d,

1

²J_CP= 16.1 Hz, C ortho), 133.1 (d, J_CP= 19.6 Hz, C

ipso), 194 (br, CO), 260 (br, C(O)CH₃). IR (CD₂Cl₂,

cm^ꢀ1): m_C@O1608 (m) and m_CO1997 (s).

12.5.5. mer,trans-[Fe(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂(COMe)]I (34)

A

dichloromethane solution of 17a/b (400 mg,

12.5.2. mer,trans-[Ru(CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂(COMe)]I (31)

0.5 mmol) was stirred under a CO atmosphere for

48 h. ¹H NMR (CD₂Cl₂, 298 K): 1.2–1.5 (m,

–P[OCH(CH₃)₂]₂), 1.8–2.6 (m, –PCH₂CH₂CH₂P–),

2.68 (s, Fe-C(O)CH₃), 4.57 and 4.78 (sept., ³J_HP= 6 Hz,

–P[OCH(CH₃)₂]₂), 7–7.9 (m, –P(C₆H₅)). ³¹P{¹H} NMR

A dichloromethane solution of 14a/14b (250 mg,

0.3 mmol) was stirred for 48 h. ¹H NMR (CD₂Cl₂,

298 K): 1–2.6 (m, –PCH₂CH₂CH₂P–, –O–CH(CH₃)₂

and –P(C₆H₁₁)), 2.4 (s, –C(O)CH₃), 4.4–4.8 (m, –O–

CH(CH₃)₂). ³¹P{¹H} NMR (CD₂Cl₂, 298 K): ꢀ4.1 (t,

2

(CD₂Cl₂, 298 K): 4 (t, J_PP= 90 Hz, –P(C₆H₅)), 175 (d,

²J_PP= 90 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR

(CD₂Cl₂, 298 K): 18.9 (m, –CH₂CH₂CH₂–), 24.7 (m,

–CH(CH₃)₂), 25.1 (m, –CH₂CH₂CH₂–P(C₆H₅)), 27.3

(dt, J_CP= 4.2, 16.3 Hz, –CH₂CH₂CH₂–P[OCH-

(CH₃)₂]₂), 48.2 (m, Fe-C(O)CH₃), 73.8 and 74.6

2

²J_PP= 50 Hz, –P(C₆H₁₁)), 154.5 (d, J_PP= 50 Hz,

–P[OCH(CH₃)₂]₂). ¹³C{¹H} NMR (CD₂Cl₂, 298 K):

18.8 (m, –CH₂CH₂CH₂–), 24.6 (m, –CH(CH₃)₂), 25.5

(m, –CH₂CH₂CH₂–P(C₆H₁₁)), 26.2 (s, cyclohexyl C

3

para), 27.2 (d, J_CP= 10.3 Hz, cyclohexyl C meta),

27.7 (m, –CH₂CH₂CH₂-P[OCH(CH₃)₂]₂), 28.3 (d,

2

(m, –P[OCH(CH₃)₂]₂), (Phenyl: 129.3 (d, J_CP= 9 Hz,

3

C ortho), 131.1 (d, J_CP= 7.7 Hz, C meta), 131.4 (s, C

1

²J_CP= 3 Hz, cyclohexyl C ortho), 38.6 (d, J_CP

=

1

para), 135.7 (d, J_CP= 40.1 Hz, C ipso), 205.8 (dt,

26.6 Hz, cyclohexyl C ipso), 49.9 (s, –C(O)-CH₃), 73.6

(m, –P[OCH(CH₃)₂]₂), 195.4 (q, ²J_P= 10.4 Hz, CO),

²J_CP= 17, 14 Hz, Fe-CO) and 208.8 (dt, J_CP= 25,

2

27.6 Hz, Fe-CO), 268 (dt, J_CP= 13, 25 Hz, Fe-

2

258.8 (dt, J_CP= 7, 13.1 Hz, –C(O)CH₃). IR (CD₂Cl₂,

C(O)CH₃)). IR (CD₂Cl₂, cm¹): m_C@O1612 (m) and m_CO

1997 (s).

cm^ꢀ1): m_C@O1612 (m) and m_CO1995 (s).

12.5.3. mer,trans-[Ru(PhP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂(COMe)]I (32)

12.5.6. mer,trans-[Fe(CyP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)-

(CO)₂(COMe)]I (35)

A

dichloromethane solution of 15a/b (400 mg,

A

dichloromethane solution of 18a/b (370 mg,

1

0.6 mmol) was stirred for 48 hours. H NMR (CD₂Cl₂,

298 K): 1.6–2.6 (m, –CH₂CH₂CH₂–), 2.47 (s, C(O)CH₃).

3.6–4.1 (m, –P(OCH₃)₂), 7.4–7.7 (m, –P(C₆H₅)). ³¹P

0.5 mmol) was stirred under a CO atmosphere for 48

hours. ¹H NMR (CD₂Cl₂, 298 K): 1.1–2.1 (m,

–PCH₂CH₂CH₂P–

and

–P(C₆H₁₁)),

1.27

(m,

–P[OCH(CH₃)₂]₂), 2.54 (s, –C(O)CH₃), 4.5 and 4.7

{¹H} NMR (CD₂Cl₂, 298 K): ꢀ12.3 (t, J_PP= 51.9 Hz,

2

–P(C₆H₅)), 168.5 (d, J_PP= 51.9 Hz, –P(OCH₃)₂).

(sept., J_HP= 6 Hz, –P[OCH(CH₃)₂]₂). ³¹P{¹H} NMR

3

¹³C{¹H}

NMR

(CD₂Cl₂,

298 K):

17.6

(m,

2

(CD₂Cl₂, 298 K): 10.7 (t, J_PP= 88 Hz, –P(C₆H₁₁)),

175.2 (d, J_PP= 88 Hz, –P[OCH(CH₃)₂]₂). ¹³C{¹H}

2

–CH₂CH₂CH₂–), 23.9 (dt, J_CP= 31.9, 3.3 Hz,

–CH₂CH₂CH₂–P(C₆H₁₁)), 27.4 (m, –CH₂CH₂CH₂–

P(OCH₃)₂), 50.6 (s, C(O)CH₃), 54.3 (m, –P(OCH₃)₂),

NMR (CD₂Cl₂, 298 K): 19 (m, –CH₂CH₂CH₂–), 24.6

(m, –CH(CH₃)₂), 25.7 (s, cyclohexyl C para), 26.2 (dt,

J_CP= 19.7, 6.3 Hz, –CH₂CH₂CH₂–P(C₆H₁₁)), 27.9 (d,

³J_CP= 3.6 Hz, cyclohexyl

3

(Phenyl: 129.3 (d, J_CP= 10.2 Hz, C meta), 129.6 (s, C

2

para), 133 (d, J_CP= 14.4 Hz, C ortho), 136.1 (d,

C

meta), 28.6 (d,

1454

P. Jaunky et al. / Journal of Organometallic Chemistry 690 (2005) 1429–1455

²J_CP= 3.8 Hz, cyclohexyl C ortho), 31.8 (dt, J_CP= 12.5,

2.2 Hz, –CH₂CH₂CH₂–P[OCH(CH₃)₂]₂), 37.4 (d,

¹J_CP= 20.6 Hz, cyclohexyl C ipso), 50.1 (m, C(O)CH₃),

73.8 (m, -P[OCH(CH₃)₂]₂), 209.8 (dt, J = 13, 29.2 Hz,

CO), 253.3 (dt, J = 10.7, 18.9 Hz, –C(O)CH₃). IR

(CD₂Cl₂, cm^ꢀ1): m_CO1616 (m), 1989 (s).

[Fe(CD₃)(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)(CO)₂]I

(40):

2D NMR (CH₃CN, 298 K): ꢀ 0.2 (br, Fe-CD₃). mer,

trans-[Fe(¹³CH₃)(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)(CO)₂]I

(41): ¹³C{¹H} NMR (CD₃CN, 298 K): ꢀ11 (q, J_CP

=

2

22.6 Hz, Fe-¹³CH₃).

Acknowledgement

12.5.7. mer,trans- [Fe(PhP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂(COMe)]I (36)

The ﬁnancial support of the Swiss National Funds

and the funds of the University of Zurich are gratefully

acknowledged. Hoechst Knapsack is gratefully acknowl-

edged for a generous gift of dichloromethylphosphine.

A

dichloromethane solution of 19a/b (250 mg,

0.4 mmol) was stirred under a CO atmosphere for

48 h. ¹H NMR (CD₂Cl₂, 298 K): 1.7–2.7 (m,

–PCH₂CH₂CH₂P–), 2.61 (s, Fe-C(O)CH₃), 3.5–4.0 (m,

–P(OCH₃)₂), 7.4–7.7 (m, –P(C₆H₅)). ³¹P{¹H} NMR

2

(CD₂Cl₂, 298 K): 2.7 (t, J_PP= 85.8 Hz, –P(C₆H₅)),

2

191.7 (d, J_PP= 85.8 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR

References

(CD₂Cl₂, 298 K): ¹³C{¹H} NMR (CD₂Cl₂, 298 K):

18.5 (m, –CH₂CH₂CH₂–), 23.9 (m, –CH(CH₃)₂), 25.6

(m, –CH₂CH₂CH₂–P(C₆H₅)), 50.1 (m, Fe-C(O)CH₃),

52–54 (m, –P(OCH₃)₂), (Phenyl: 129 (s, C para), 130.4

(d, J_CP= 9 Hz, C meta), 134.1 (d, J_CP= 9 Hz, C

1

ortho), 136 (d, J_CP= 40 Hz, C ipso), 208 (br, Fe-CO),

267.2 (m, Fe-C(O)CH₃)). IR (CD₂Cl₂, cm^ꢀ1): m_C@O

1614 (m), m_CO1984 (s).

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12.5.8. mer,trans-[Fe(CyP[CH₂CH₂CH₂P(OMe)₂]₂)-

(CO)₂(COMe)]I (37)

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Sect. B J. Chem. Sci. 42 (1987) 171.

A dichloromethane solution of 20a/20b (250 mg,

0.4 mmol) was stirred under a CO atmosphere for 48

hours. ¹H NMR (CD₂Cl₂, 298 K): 1.1–2 (m,

–PCH₂CH₂CH₂P– and –P(C₆H₁₁)), 2.53 (s, Fe-

C(O)CH₃), 3.5–4.0 (m, –P(OCH₃)₂). ³¹P{¹H} NMR

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(2000) 2053.

2

(CD₂Cl₂, 298 K): 9.7 (t, J_PP= 85.5 Hz, –P(C₆H₁₁)),

2

[14] Z.S. Novikova, A.A. Prishchenko, I.F. Lutsenko, Zh. Obsh.

Khim. 47 (1977) 707.

192.3 (d, J_PP= 85.5 Hz, –P(OCH₃)₂). ¹³C{¹H} NMR

(CD₂Cl₂, 298 K): 19 (m, –CH₂CH₂CH₂–), 25.9 (s, cyclo-

hexyl C para), 26.6 (m, –CH₂CH₂CH₂–P(C₆H₁₁)), 27.8

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(d, ³J_CP= 4.1 Hz, cyclohexyl

C

ortho), 33.2 (dt,

meta), 28 (d,

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Trans. I (1973) 2226.

²J_CP= 3.7 Hz, cyclohexyl

C

J_CP= 12.5, 2.2 Hz, –CH₂CH₂CH₂–P(OCH₃)₂), 37.4 (d,

¹J_CP= 21.8 Hz, cyclohexyl C ipso), 48.7 (m, C(O)CH₃),

51–54 (m, –P(OCH₃)₂), 211 (br, Fe-CO), 259.2 (m, Fe-

C(O)CH₃)). IR (CD₂Cl₂, cm^ꢀ1): m_C@O1616 (m), m_CO

1973 (s).

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38 and 39 were prepared from the reaction of 40 and

41, respectively, with CO. The D and ¹³C labelled com-

plexes 40 and 41 were prepared in an analogous fashion

to compounds 17a/b, in similar yields, from the reaction

of 5 (300 mg, 0.5 mmol) with CD₃I or ¹³CH₃I (0.15 mL,

2.5 mmol). mer,trans- [Fe(PhP[CH₂CH₂CH₂P(Oi-Pr)₂]₂)

(CO)₂(COCD₃)]I (38): 2D NMR (CH₃CN, 298 K): 2.6

(s, Fe-COCD₃). mer,trans-[Fe(PhP [CH₂CH₂CH₂P(Oi-

Pr)₂]₂)(CO)₂( CO¹³CH₃)]I (39): ¹³C{¹H} NMR

(CD₃CN, 298 K): 48 (s, Fe-¹³COCH₃). mer,trans-

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1455

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Iron(0) and ruthenium(0) complexes with tridentate phosphonite ligands and their potential for ketene formation from methyl iodide, CO and a base

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