Areneruthenium(II) complexes containing bulky phosphines with various functionalities as ligands

Article abstract of DOI:10.1039/b208891f

The dimeric starting materials [Ru(η⁶-arene)Cl₂]₂ (arene = mes, C₆Me₆) react with the functionalized phosphines Prⁱ ₂PCH₂X (X = CH₂OMe, CO₂Me) to

Full text of DOI:10.1039/b208891f

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Areneruthenium(II) complexes containing bulky phosphines with
various functionalities as ligands†
Gerhard Henig, Michael Schulz, Bettina Windmüller and Helmut Werner*
Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-97074 Würzburg,
Germany. E-mail: helmut.werner@mail.uni-wuerzburg.de
Received 11th September 2002, Accepted 19th November 2002
First published as an Advance Article on the web 3rd January 2003
The dimeric starting materials [Ru(η6-arene)Cl2]2 (arene = mes, C6Me6) react with the functionalized phosphines
Pri2PCH2X (X = CH2OMe, CO2Me) to give the mononuclear compounds [Ru(η6-arene)(κP-Pri2PCH2X)Cl2] 3–6
which upon treatment with AgPF6 afford the chelate complexes [Ru(η6-arene)(κ2P,O-Pri2PCH2CH2OMe)Cl]PF6
7, 8 and [Ru(η6-arene){κ2P,O-Pri2PCH2C(O)OMe}Cl]PF6 9, 10, respectively. Complexes 7 and 8 react with CO
and CNBut to yield the chiral-at-metal compounds [Ru(η6-arene)(κP-Pri2PCH2CH2OMe)(L)Cl]PF6 11–14.
Treatment of 8 (arene = C6Me6) with Na2CO3 in the presence of water produces the carbonatoruthenium()
derivative [Ru(η6-C Me )(κ2O,O-O C᎐O)(κP-Pri PCH CH OMe)] 17. The reaction of 9 (arene = mes) with
᎐
6
6
2
2
2
2
KOBut leads to the formation of the uncharged phosphinoester enolate complex [Ru(η6-mes)(κ2P,O-Pri PCH᎐
᎐
2
C(O)OMe)Cl] 18 which in benzene at room temperature smoothly rearranges to the phosphinomethanide isomer
[Ru(η6-mes)(κ2P,C-Pri2PCHCO2Me)Cl] 19. The corresponding phosphinoacetate complexes [Ru(η6-arene)-
{κ2P,O-Pri PCH C(᎐O)O}Cl] 21, 22 were obtained as the major products from 5 or 6 and NaH/Al O in THF.
᎐
2
2
2
3
Compound 18 reacts with water by ester hydrolysis to form 21 and with phenylisocyanate and diphenylketene to
afford 24 and 25 by insertion of the heterocumulene into the enolate C–H bond. The molecular structures of 19
and 25 were determined crystallographically.
Recently, we have been interested in the synthesis and reactivity
of transition-metal complexes containing phosphino-ethers,
-amines and -esters as ligands.1 The characteristic feature of
these ligands is that they behave as hemilabile chelating
units and even under mild conditions are able to create a free
coordination site to which a reactive substrate can be added.2
Moreover, phosphino-esters and -ketones are easily converted
in the coordination sphere of a transition-metal to phosphino-
enolates, the metal complexes of which play an important role
in homogeneous catalysis.3
As a continuation of our work on half-sandwich-type com-
pounds with functionalized phosphines,4 we describe in this
paper the preparation of a series of neutral and cationic η6-
mesitylene- and η6-hexamethylbenzeneruthenium() complexes
with Pri2PCH2CH2OMe and Pri2PCH2CO2Me as ligands. We
also illustrate that the coordinated phosphinoester is not
only easily deprotonated but that, quite unexpectedly, from
the isomeric forms Pri PCH᎐C(OR)OϪ and Pri PCHCO RϪ the
᎐
2
2
2
second one, forming a three-membered chelate ring with the
metal, is the more stable. Some preliminary results of this work
have already been communicated.5
Results and discussion
Neutral and cationic complexes with Pri2PCH2CH2OMe and
Pri2PCH2CO2Me as mono- and bi-dentate ligands
Scheme 1
Similarly to PPri3 and other tertiary phosphines, the chloro-
bridged dimers 1 and 2 also react with Pri2PCH2CH2OMe and
Pri2PCH2CO2Me by bridge-splitting to give the mononuclear
products 3, 4 and 5, 6 in excellent yields (Scheme 1). These are
orange to red solids which are practically air-stable and readily
soluble in polar organic solvents such as CH2Cl2, THF or
Treatment of the dichloro compounds 3–6 with an equimolar
amount of AgPF6 in CH2Cl2 results in the abstraction of one
chloride to give the cationic complexes 7–10 in 80–90% isolated
yield. The composition of the slightly air-sensitive solids has
been confirmed not only by elemental analysis but also by con-
ductivity measurements. In contrast to 7, in the 1H NMR spec-
trum of 8 at room temperature the signals for the methine and
methyl protons of the isopropyl groups and for the PCH2CH2
methylene protons are significantly broadened and neither a
P,H nor a H,H coupling can be observed. However, at 248 K the
1H NMR spectrum of 8 displays two septets for the PCH and
four doublets-of-doublets for the CHCH3 protons which is in
agreement with the rigid structure shown in Scheme 1. By
1
nitromethane. While the H and 31P NMR data of 3–6 deserve
no further comment, we note that the single resonance in the 31
P
NMR spectra is shifted ca. 30–40 ppm downfield compared
with the free phosphines Pri2PCH2CH2OMe and Pri2PCH2-
CO2Me, respectively.
† Dedicated with great sympathy to Professor Peter M. Maitlis on the
occasion of his 70th birthday.
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
D a l t o n T r a n s . , 2 0 0 3 , 4 4 1 – 4 4 8
441

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increasing the temperature to 350 K only one resonance for the
PCH and two resonances for the CHCH3 protons appear. The
most reasonable explanation for the temperature dependence of
the 1H NMR spectrum of 8 is that the compound is fluxional in
solution. At room temperature and above, a rapid opening and
re-closing of the chelate ring occurs, thereby creating on aver-
age an effective mirror plane that makes the PCH and half of
the CHCH3 protons become equivalent. This behaviour is not
unusual and has been observed in various cases in particular by
Lindner,2 Braunstein,7 and also by us.1
instead the carbonatoruthenium() complex 17 (see Scheme 2).
The light yellow air-stable solid was isolated in 67% yield. Since
in contrast to the cationic precursor 8 the neutral molecule 17 is
not chiral, the 1H NMR spectrum shows only one signal for the
PCH and two signals (doublets-of-doublets) for the CHCH3
protons of the isopropyl groups.
Phosphinomethanide versus phosphinoenolate: thermodynamic
preference of the three-membered chelate ring
Similarly to structurally related areneosmium complexes,6 the
cationic species 9 also reacts with KOBut in THF to give the
phosphinoenolate compound 18 as a light red, slightly air-
sensitive solid in 78% yield (Scheme 3). The composition of 18
The hemilabile nature of the phosphine ligand in compounds
7 and 8 is illustrated by the reactions summarized in Scheme 2.
Scheme 3
was confirmed by elemental analysis and the mass spectrum.
The most characteristic feature of the 1H NMR spectrum of 18
is the signal at δ 3.19 for the vinylic proton which is split into a
doublet due to P,H coupling. The 13C NMR spectrum of 18
displays two resonances for the O–C–C–P carbon atoms of the
chelate ring at δ 180.5 (O–C) and 44.5 (C–P), the chemical shift
and the P,C coupling constant of which are similar to those of
other phosphinoester enolate-metal derivatives.6–8
While most of the phosphinoenolate complexes, such as
those used for the oligomerization and polymerization of
alkenes,3,9 seem to be quite stable, compound 18 is thermally
labile and slowly (3 d) rearranges in benzene at room temper-
ature to give the isomer 19. The 1H NMR spectrum of 19
(which is a yellow air-stable solid) shows a doublet at δ 2.71 for
the CHCO2Me proton and the 13C NMR spectrum a singlet at
δ 10.0 for the carbon atom of the RuCP ring.
Scheme 2
Treating solutions of the starting materials in acetone or di-
chloromethane with CO or CNBut leads to a smooth cleavage
of the Ru–O bond and gives the 1 : 1 adducts 11–14 containing
a monodentate phosphine as light yellow solids in 84–91%
yield. Similarly to the related carbonylosmium complex [Os(η6-
mes)(κP-Pri2PCH2CH2OMe)(CO)Cl]PF6,6 both the ruthenium
counterpart 11 and the hexamethylbenzene analogue 12 are
relatively labile; they decompose in solution within 1–2 hours
in the absence of a CO atmosphere. In contrast, the related
isocyanide derivatives 13 and 14 are quite stable and can be
stored under argon for weeks. We assume that the increase in
the thermodynamic stability when CO is replaced by CNBut is
attributed to the stronger donor ability of the isocyanide, which
is also reflected in the shift of the phosphorus resonance by
10–20 ppm to higher field in the 31P NMR spectra of 13, 14
compared to those of 11 and 12.
The structural proposal for 19 outlined in Scheme 3 was con-
firmed by an X-ray crystal structure analysis. As the ORTEP
drawing (Fig. 1) reveals, the ruthenium atom is coordinated by
the mesitylene ring, one chloride and the P,C-bonded phos-
phinomethanide ligand, the CO2Me substituent of which is
pointing away from the Ru–Cl axis. As anticipated, the bond
angle P–Ru–C(1) is significantly smaller than the bond angles
P–Ru–Cl and Cl–Ru–C(1), the values being similar to those
found in various M(κ2P,C-R2PCH2) derivatives.10 The distance
P–C(1) is shorter, by ca. 0.08 Å, than the distances P–C(4) and
P–C(7) (see Table 1) which indicates a substantial double-bond
character of the phosphorus–carbon bond in the RuCP unit.
The phosphinomethanide- and not the isomeric phosphino-
esterenolate-ruthenium() complex is also formed, although
as the minor component, on treatment of 5 with NaH/Al2O3 in
THF (Scheme 4). The hexamethylbenzene derivative 6 behaves
analogously. In both cases, the main product of the reaction is
the corresponding phosphinocarboxylate compound 21 or 22,
respectively. The IR and 1H NMR data of 21 and 22 are similar
to those of the half-sandwich-type complex [Ru(η6-mes)-
Compared with CO and tert-butylisocyanide, acetonitrile
behaves differently toward 7 and 8. If a solution of the corre-
sponding chelate complex in CH2Cl2 is treated with excess
CH3CN, stirred for 5 min and the solvent is then removed
rather quickly, the H and 13C NMR spectra confirm the pres-
1
ence of mixtures of 7 and 15 or of 8 and 16, respectively.
Attempts to separate the two components by column chrom-
atography or re-crystallization from CH2Cl2/hexane led to the
re-isolation of the starting material. Since a re-conversion of 15
to 7 and of 16 to 8 also occurs by storing the mixtures under
argon, we conclude that the entropic contribution due to chel-
ation and not the donor capability of N versus O is the dominat-
ing component. That in the reaction mixtures of 7/15 and 8/16
the acetonitrile compounds are present, is indicated both by the
᎐
NMR and IR spectra, the latter displaying a strong ν(C᎐N)
᎐
band at 2260 (15) and 2264 cmϪ1 (16), respectively.
{κ2P,O-Ph PCH C(᎐O)O}Cl] which was generated by acid
᎐
2
2
The reaction of 8 with Na2CO3, undertaken to find out
whether a deprotonation of the PCH2 unit or of one of the
methyl groups of the six-membered ring is possible, affords
hydrolysis of [Ru(η6-mes)(κP-Ph2PCH2CO2But)Cl2].11 In this
context we note that in contrast to 5 the related osmium com-
pound [Os(η6-mes)(κP-Pri2PCH2CO2Me)Cl2] reacts with NaH/
D a l t o n T r a n s . , 2 0 0 3 , 4 4 1 – 4 4 8
442

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Table 1 Selected bond lengths (Å) and angles (Њ) for compound 19
does not lead to cleavage of the O–CH3 bond of the ester enol-
ate moiety but produces instead by protonation of the PCH
carbon atom the dichloro complex 5 quantitatively (Scheme 5).
Ru–C(1)
Ru–P
Ru–Cl
Ru–C(10)
Ru–C(11)
Ru–C(12)
2.201(2)
2.2694(8)
2.4101(8)
2.230(2)
2.243(2)
2.259(2)
Ru–C(13)
Ru–C(14)
Ru–C(15)
P–C(1)
C(1)–C(2)
C(2)–O(1)
2.242(2)
2.188(2)
2.168(2)
1.761(2)
1.455(3)
1.208(3)
Cl–Ru–P
88.97(3)
84.97(6)
46.37(6)
64.77(7)
Ru–C(1)–P
68.86(7)
128.6(2)
110.0(2)
121.3(2)
Cl–Ru–C(1)
P–Ru–C(1)
Ru–P–C(1)
C(1)–C(2)–O(1)
C(1)–C(2)–O(2)
O(1)–C(2)–O(2)
Scheme 5
While the chelate compound 18 is inert toward CO2, it reacts
with phenylisocyanate in benzene to yield a mixture of prod-
ucts, among which the functionalized enolate complex 24 is the
dominating species. This derivative of 18 formally results from
the addition of the C–H bond of the phosphinoester enolate
across the C᎐N bond of the substrate. Insertion reactions of
᎐
this type are not without precedent and have been studied in
detail, particularly by Braunstein, Matt and their coworkers.15
Typical spectroscopic features of 24 are the N–H stretching
mode at 3390 cmϪ1 in the IR and the signal for the N–H proton
at δ 9.01 in the 1H NMR spectrum.
Fig. 1 An ORTEP plot of compound 19.21
Not only phenylisocyanate but also diphenylketene reacts
with the enolate complex 18 in hexane/dichloromethane at
room temperature to afford the 1 : 1 adduct 25 in 67% isolated
yield (see Scheme 5). The composition of the orange, slightly
air- and moisture-sensitive solid has been substantiated not
only by elemental analysis but also by X-ray crystallography.
The presence of the un-coordinated CO2Me group is indicated
by the ν(C᎐O) absorption at 1677 cmϪ1 in the IR spectrum and
᎐
by the singlet resonance at δ 191.0 in the 13C NMR spectrum.
The signal for the C–O enolate carbon atom appears at δ 181.6
and is split into a doublet due to P,C coupling.
The result of the single-crystal X-ray structure analysis of
25 is shown in Fig. 2 with selected bond lengths and angles in
Table 2. As the ORTEP drawing reveals the molecule possesses
a similar piano-stool configuration as the phosphinomethanide
complex 19. However, due to the existence of a five-membered
Scheme 4
Al2O3 in THF to give the corresponding phosphinomethanide
complex almost quantitatively.12
Treatment of 19 with HBF4 in ether leads to the cleavage
of the Ru-C bond and affords the tetrafluoroborate of the
Ϫ
cationic chelate compound 23. The analogous PF6 salt was
prepared prior to this experiment from 5 and AgPF6 (see
Scheme 1). Addition of excess [HNEt3]Cl to a solution of
23 in dichloromethane re-generates the dichlororuthenium()
derivative 5.
Reactions of the phosphinoester enolate complex 18
The phosphinocarboxylate compound 21, being the major
product in the reaction of 5 with NaH/Al2O3 (see Scheme 4), is
formed exclusively upon hydrolysis of the ester enolate function
of 18 in acetone solution. A similar metal-assisted trans-
formation of a phosphinoester enolate to a corresponding
phosphinoacetate was recently observed by us13 as well as by
Braunstein et al.14 in the case of square-planar iridium() and
palladium() derivatives. Treatment of 18 with HCl in benzene
Fig. 2 An ORTEP plot of compound 25.21
D a l t o n T r a n s . , 2 0 0 3 , 4 4 1 – 4 4 8
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Table 2 Selected bond lengths (Å) and angles (Њ) for compound 25
separated from the mother liquor, washed twice with hexane
(5 cm3) and dried: yield 738 mg (88%); mp 140 ЊC (decomp.)
(Found: C, 45.89; H, 6.93. C18H33Cl2OPRu requires C, 46.16; H,
7.10%). NMR (CDCl3): δH (200 MHz) 5.06 (3 H, s, C6H3), 3.64
(2 H, m, CH2OMe), 3.27 (3 H, s, OCH3), 2.54 (2 H, m,
PCHCH3), 2.26 (2 H, m, PCH2), 2.19 (9 H, s, CH3 of mes), 1.30
Ru–P
Ru–Cl
Ru–O(1)
Ru–C(24)
Ru–C(25)
Ru–C(26)
2.3349(19)
2.404(2)
2.057(4)
2.189(6)
2.249(6)
2.298(6)
Ru–C(27)
Ru–C(28)
Ru–C(29)
P–C(1)
O(1)–C(2)
C(1)–C(2)
2.184(7)
2.233(6)
2.198(6)
1.784(7)
1.277(6)
1.392(8)
3
3
[6 H, dd, J(P,H) 14.2, J(H,H) 7.3, PCHCH3], 1.29 [6 H, dd,
3
3J(P,H) 13.1, J(H,H) 7.1, PCHCH3]; δC (50.3 MHz) 101.5 [d,
Cl–Ru–P
89.49(8)
84.04(11)
79.71(11)
101.4(2)
123.7(4)
P–C(1)–C(2)
P–C(1)–C(3)
O(1)–C(2)–C(1)
O(1)–C(2)–C(5)
C(1)–C(2)–C(5)
112.8(5)
123.6(5)
122.3(6)
114.4(5)
123.3(6)
2J(P,C) 2.6, CCH3 of mes], 84.7 [d, 2J(P,C) 3.7, CH of mes], 69.1
(s, CH2OMe), 58.2 (s, OCH3), 27.0 [d, 1J(P,C) 22.0, PCHCH3],
20.8 [d, 1J(P,C) 24.6, PCH2], 19.9, 19.3 (both s, PCHCH3), 18.8
(s, CH3 of mes); δP (81.0 MHz) 34.1 (s).
Cl–Ru–O(1)
P–Ru–O(1)
Ru–P–C(1)
Ru–O(1)–C(2)
[Ru(ꢀ6-C6Me6)(ꢁP-Pri2PCH2CH2OMe)Cl2] 4. This com-
pound was prepared as described for 3 from 2 (663 mg, 0.99
mmol) and Pri2PCH2CH2OMe (500 mg, 2.84 mmol) in CH2Cl2
(40 cm3). Light red solid: yield 815 mg (80%), mp 130 ЊC
(decomp.) (Found: C, 48.85; H, 7.41. C21H39Cl2OPRu requires
C, 49.41; H, 7.10%). NMR (CDCl3): δH (200 MHz) 3.59 (2 H,
m, CH2OMe), 3.30 (3 H, s, OCH3), 2.51 (2 H, m, PCHCH3),
2.20 (2 H, s, PCH2), 2.01 (18 H, s, CH3 of C6Me6), 1.32 [6 H, dd,
chelate ring, the three bond angles between the three
“legs” deviate much less from the 90Њ value than in the case of
19. The cyclic phosphinoenolate-metal unit is almost planar,
with the carbon atoms C(3) and C(5) of the substituents lying
in the ring plane. While the bond length C(1)–C(2) [1.392(8) Å]
is only somewhat elongated compared to a normal C᎐C bond,
᎐
the distance C(2)–O(1) [1.277(6) Å] lies between that of a C–O
single and a C᎐O double bond, indicating some electron
3
3
3J(P,H) 13.4, J(H,H) 7.0, PCHCH3], 1.24 [6 H, dd, J(P,H)
᎐
delocalization within the enolate fragment.
13.1, 3J(H,H) 7.0, PCHCH3]; δP (81.0 MHz) 27.6 (s).
[Ru(ꢀ6-mes)(ꢁP-Pri2PCH2CO2Me)Cl2] 5. This compound
was prepared as described for 3 from 1 (499 mg, 0.85 mmol) and
Pri2PCH2CO2Me (450 mg, 2.37 mmol) in CH2Cl2 (40 cm3).
Orange–red solid: yield 745 mg (91%), mp 160 ЊC (decomp.)
(Found: C, 45.13; H, 6.73. C18H31Cl2O2PRu requires C, 44.82;
Conclusions
The work presented in this paper has shown that bulky func-
tionalized phosphines of the general composition Pri2PCH2X
with X = CH2OMe and CO2Me can behave in half-sandwich-
type areneruthenium() compounds as mono- as well as bi-
dentate ligands. Not unexpectedly, the interaction between the
functional group X of the phosphine and the metal is more
labile for M = Ru than for M = Os which is illustrated in the
rapid and complete conversion of 7 and 8 to the carbonyl com-
plexes 11 and 12 and in the (reversible) formation of 15 and 16,
respectively. The related osmium precursor [Os(η6-mes)(κ2P,
O-Pri2PCH2CH2OMe)Cl]PF6 is inert toward acetonitrile.16
However, the most remarkable result of our investigations is
that, regarding the compounds 18 and 19, the complex with the
three-membered chelate ring is thermodynamically more stable
than the isomer with the five-membered ring. There is, to the
best of our knowledge, no precedence for a reaction like that
from 18 to 19 which also has no analogy in osmium chemistry.12
We assume that the driving force for the unusual isomerization
process is the re-formation of the intact CO2Me unit.
H, 6.48%). IR (KBr): ν(C᎐O) 1719 cmϪ1. NMR (CDCl3):
᎐
δH (200 MHz) 5.21 (3 H, s, C6H3), 3.58 (3 H, s, OCH3), 3.31
[2 H, d, 2J(P,H) 10.6, PCH2], 2.70 (2 H, m, PCHCH3), 2.19 (9 H,
s, CH3 of mes), 1.35 [6 H, dd, 3J(P,H) 15.5, 3J(H,H) 7.2,
PCHCH3], 1.22 [6 H, dd, 3J(P,H) 13.6, 3J(H,H) 7.0, PCHCH3];
δP (81.0 MHz) 41.6 (s).
[Ru(ꢀ6-C6Me6)(ꢁP-Pri2PCH2CO2Me)Cl2] 6. This compound
was prepared as described for 3 from 2 (721 mg, 1.08 mmol) and
Pri2PCH2CO2Me (700 mg, 3.68 mmol) in CH2Cl2 (40 cm3).
Light red solid: yield 1.005 g (89%), mp 144 ЊC (decomp.)
(Found: C, 47.60; H, 6.72. C21H37Cl2O2PRu requires C, 48.09;
H, 7.11%). IR (KBr): ν(C᎐O) 1722 cmϪ1. NMR (CDCl3):
᎐
2
δH (200 MHz) 3.58 (3 H, s, OCH3), 3.28 [2 H, d, J(P,H) 10.2,
PCH2], 2.57 (2 H, m, PCHCH3), 2.05 (18 H, s, CH3 of C6Me6),
3
3
1.30 [6 H, dd, J(P,H) 15.3, J(H,H) 7.3, PCHCH3], 1.23 [6 H,
dd, 3J(P,H) 13.3, 3J(H,H) 7.4, PCHCH3]; δP (81.0 MHz) 38.8 (s).
[Ru(ꢀ6-mes)(ꢁ2P,O-Pri2PCH2CH2OMe)Cl]PF6 7. A solution
of compound 3 (303 mg, 0.65 mmol) in CH2Cl2 (15 cm3) was
treated with a solution of AgPF6 (164 mg, 0.65 mmol) in
CH2Cl2 (10 cm3) and stirred for 45 min at room temperature.
The reaction mixture was filtered with Celite and the filtrate was
evaporated to dryness in vacuo. The oily residue was washed
three times with ether (5 cm3) and stored at Ϫ20 ЊC for 12 h. An
orange microcrystalline solid was obtained: yield 338 mg (90%);
mp 135 ЊC (decomp.) (Found: C, 37.05; H, 5.61; Ru, 17.44.
C18H33ClF6OP2Ru requires C, 37.41; H, 5.76; Ru, 17.49%). Λ 75
cm2 ΩϪ1 molϪ1. NMR (CDCl3): δH (400 MHz) 5.45 (3 H, s,
C6H3), 3.90 (3 H, s, OCH3), 3.39 (2 H, m, CH2OMe), 2.84, 2.77
(1 H each, both m, PCHCH3), 2.26 (9 H, s, CH3 of mes), 1.78
(2 H, m, PCH2), 1.47, 1.45, 1.30, 1.29 (3 H each, all m,
PCHCH3); δP (162.0 MHz) 67.4 (s, PPri2), Ϫ144.3 [sept, 1J(P,F)
712.7, PF6Ϫ].
Experimental
All experiments were carried out under an atmosphere of
argon by Schlenk techniques. The starting materials 1,17 2,18
Pri2PCH2CH2OMe,1a and Pri2PCH2CO2Me,1a were prepared
as described in the literature. NMR spectra were recorded at
room temperature on Bruker AC 200 and Bruker AMX 400
instruments, IR spectra on a Perkin-Elmer 1420 or an IFS 25
FT-IR spectrometer, and mass spectra on a Finnigan 90 MAT
instrument (70 eV). Melting points were measured by DTA.
The conductivity Λ was determined in nitromethane with a
Schott Konduktometer CG 851. Abbreviations used: s, singlet;
d, doublet; sept, septet; m, multiplet; br, broadened signal;
coupling constants J in Hz.
Preparations
[Ru(ꢀ6-mes)(ꢁP-Pri2PCH2CH2OMe)Cl2] 3. A suspension of
compound 1 (523 mg, 0.90 mmol) in CH2Cl2 (40 cm3) was
treated with Pri2PCH2CH2OMe (500 mg, 2.84 mmol) and
stirred for 3 h at room temperature. The reaction mixture was
filtered with Celite and the filtrate was concentrated to ca. 3 cm3
in vacuo. After the solution was layered with hexane (15 cm3),
an orange–red microcrystalline solid precipitated which was
[Ru(ꢀ6-C6Me6)(ꢁ2P,O-Pri2PCH2CH2OMe)Cl]PF6 8. This
compound was prepared as described for 7 from 4 (167 mg, 0.27
mmol) and AgPF6 (68 mg, 0.27 mmol) in CH2Cl2 (35 cm3).
Light red solid: yield 149 mg (89%), mp 150 ЊC (decomp.)
(Found: C, 40.26; H, 5.82. C21H39ClF6OP2Ru requires C, 40.68;
H, 6.34%). Λ 71 cm2 ΩϪ1 molϪ1. NMR (CDCl3): δH (400 MHz,
D a l t o n T r a n s . , 2 0 0 3 , 4 4 1 – 4 4 8
444

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293 K) 3.57 (3 H, s, OCH3), 3.44 (2 H, br, CH2OMe), 2.77 (4 H,
br, PCH2 and PCHCH3), 2.11 (18 H, s, CH3 of C6Me6), 1.71
(3 H, br, PCHCH3), 1.28 (9 H, br, PCHCH3); δH (400 MHz, 248
K) 3.58 (3 H, s, OCH3), 3.45 (2 H, m, CH2OMe), 2.85 (2 H, m,
PCH2), 2.81, 2.72 (1 H each, both sept, 3J(H,H) 7.0, PCHCH3),
C22H39ClF6O2P2Ru requires C, 40.78; H, 6.07%). Λ 72 cm2 ΩϪ1
molϪ1. IR (KBr): ν(CO) 1999 cmϪ1. NMR (CDCl3): δH (400
MHz) 3.49 (2 H, m, CH2OMe), 3.28 (3 H, s, OCH3), 2.36 (4 H,
m, PCH2 and PCHCH3), 2.24 (18 H, s, CH3 of C6Me6), 1.31,
1.29, 1.25, 1.23 (3 H each, all m, PCHCH3); δC (100.6 MHz)
3
2
2
2.12 (18 H, s, CH3 of C6Me6), 1.50 [3 H, dd, J(P,H) 15.2,
198.0 [d, J(P,C) 24.1, CO], 113.5 [d, J(P,C) 2.0, CCH3 of
3J(H,H) 7.0, PCHCH3], 1.37 [3 H, dd, 3J(P,H) 14.7, 3J(H,H) 7.0,
PCHCH3], 1.30 [3 H, dd, 3J(P,H) 15.5, 3J(H,H) 7.0, PCHCH3],
C6Me6), 67.0 (s, CH2OMe), 58.4 (s, OCH3), 28.6 [d, J(P,C)
1
25.7, PCHCH3], 28.0 [d, 1J(P,C) 26.5, PCHCH3], 22.0 [d,
3
3
2
1.22 [3 H, dd, J(P,H) 13.9, J(H,H) 7.0, PCHCH3]; δC (100.6
MHz) 95.9 [d, 2J(P,C) 2.5, CCH3 of C6Me6], 75.9 (s, CH2OMe),
68.5 (s, OCH3), 25.4 (m, PCHCH3), 22.0 [d, 1J(P,C) 23.6,
PCH2], 19.8, 18.8, 15.8 (all s, PCHCH3), 16.2 (s, CH3 of
1J(P,C) 26.7, PCH2], 20.5 (s, PCHCH3), 19.5 [d, J(P,C) 1.0,
PCHCH3], 19.2 [d, 2J(P,C) 3.9, PCHCH3], 19.1 [d, 2J(P,C) 2.7,
PCHCH3], 16.6 (s, CCH3 of C6Me6); δP (162.0 MHz) 52.0
(s, PPri2), Ϫ144.7 [sept, 1J(P,F) 712.8, PF6Ϫ].
1
C6Me6); δP (162.0 MHz) 58.4 (s, PPri2), Ϫ144.4 [sept, J(P,F)
712.8, PF6Ϫ].
[Ru(ꢀ6-mes)(ꢁP-Pri2PCH2CH2OMe)(CNBut)Cl]PF6 13.
A
solution of 7 (98 mg, 0.17 mmol) in CH2Cl2 (10 cm3) was
treated with CNBut (15 mg, 0.18 mmol) and stirred for 5 min at
room temperature. The solvent was evaporated in vacuo and to
the remaining light yellow oil ether (5 cm3) was added. After the
suspension was stirred for 1 h, a light yellow solid was obtained
which was washed twice with ether (5 cm3) and dried: yield 94
mg (84%), mp 112 ЊC (decomp.) (Found: C, 41.69; H, 6.20; N,
2.83. C23H42ClF6NOP2Ru requires C, 41.79; H, 6.40; N, 2.12%).
[Ru(ꢀ6-mes){ꢁ2P,O-Pri2PCH2C(O)OMe}Cl]PF6 9. This
compound was prepared as described for 7 from 5 (280 mg,
0.58 mmol) and AgPF6 (147 mg, 0.58 mmol) in CH2Cl2
(25 cm3). Orange–red solid: yield 308 mg (90%), mp 89 ЊC
(decomp.) (Found: C, 36.26; H, 5.11. C18H31ClF6O2P2Ru
requires C, 36.53; H, 5.28%). Λ 68 cm2 ΩϪ1 molϪ1. IR (KBr):
ν(C᎐O) 1618 cmϪ1. NMR (CDCl3): δH (400 MHz) 5.36 (3 H, s,
᎐
Λ 70 cm2 ΩϪ1 molϪ1. IR (KBr): ν(C᎐N) 2164 cmϪ1. NMR
᎐
C6H3), 3.97 (3 H, s, OCH3), 2.94 [2 H, AB part of ABX system,
δ(HA) 3.10, δ(HB) 2.78, PCH2], 2.82, 2.77 (1 H each, both m,
PCHCH3), 2.27 (9 H, s, CH3 of mes), 1.36, 1.32, 1.31, 1.25 (3 H
᎐
(CDCl3): δH (400 MHz) 5.65 (3 H, s, C6H3), 3.55 (2 H, m,
CH2OMe), 3.30 (3 H, s, OCH3), 2.46, 2.10 (1 H each, both m,
PCHCH3), 2.36 (2 H, m, PCH2), 2.29 (9 H, s, CH3 of mes), 1.57
(9 H, s, CH3 of CNBut), 1.30, 1.26, 1.25, 1.21 (3 H each, all m,
PCHCH3); δP (162.0 MHz) 47.1 (s, PPri2), Ϫ144.2 [sept, 1J(P,F)
712.8, PF6Ϫ].
2
each, all m, PCHCH3); δC (100.6 MHz) 186.2 [d, J(P,C) 10.1,
CO2], 106.8 (s, CCH3 of mes), 80.2 [d, 2J(P,C) 4.0, CH of mes],
1
1
57.1 (s, OCH3), 30.0 [d, J(P,C) 28.8, PCH2], 25.8 [d, J(P,C)
1
25.5, PCHCH3], 25.6 [d, J(P,C) 18.2, PCHCH3], 19.4 (s, CH3
2
of mes), 19.0 (s, PCHCH3), 18.4 [d, J(P,C) 1.7, PCHCH3],
17.3, 17.2 (both s, PCHCH3); δP (162.0 MHz) 66.3 (s, PPri2),
Ϫ144.2 [sept, 1J(P,F) 712.8, PF6Ϫ].
[Ru(ꢀ6-C6Me6)(ꢁP-Pri2PCH2CH2OMe)(CNBut)Cl]PF6 14.
This compound was prepared as described for 13 from 8
(81 mg, 0.13 mmol) and CNBut (40 mg, 0.48 mmol) in CH2Cl2
(10 cm3). Light yellow solid: yield 79 mg (86%), mp 120 ЊC
(decomp.) (Found: C, 44.05; H, 6.75; N, 2.71. C26H48ClF6-
NOP2Ru requires C, 44.41; H, 6.88; N, 1.99%). Λ 74 cm2 ΩϪ1
[Ru(ꢀ6-C6Me6){ꢁ2P,O-Pri2PCH2C(O)OMe}Cl]PF6 10. This
compound was prepared as described for 7 from 6 (102 mg,
0.19 mmol) and AgPF6 (49 mg, 0.19 mmol) in CH2Cl2 (25 cm3).
Red solid: yield 98 mg (81%), mp 159 ЊC (decomp.) (Found: C,
39.06; H, 5.40. C21H37ClF6O2P2Ru requires C, 39.79; H, 5.88%).
molϪ1. IR (KBr): ν(C᎐N) 2151 cmϪ1. NMR (CDCl3): δH (400
᎐
᎐
MHz) 3.43 (2 H, m, CH2OMe), 3.25 (3 H, s, OCH3), 2.78, 2.47
Λ 78 cm2 ΩϪ1 molϪ1. IR (KBr): ν(C᎐O) 1616 cmϪ1. NMR
(1 H each, both m, PCHCH3), 2.31 (2 H, m, PCH2), 2.10 (18 H,
s, CH3 of C6Me6), 1.51 (9 H, s, CH3 of CNBut), 1.20 (9 H, m,
PCHCH3), 1.12 [3 H, dd, 3J(P,H) 15.0, 3J(H,H) 7.3, PCHCH3];
᎐
(CDCl3): δH (400 MHz) 3.93 (3 H, s, OCH3), 2.93 [2 H, AB part
of ABX system, δ(HA) 3.10, δ(HB) 2.76, PCH2], 2.73 (2 H, m,
PCHCH3), 2.16 (18 H, s, CH3 of C6Me6), 1.31, 1.30, 1.26 (3 H
each, all m, PCHCH3), 1.13 [3 H, dd, 3J(P,H) 16.5, 3J(H,H) 7.2,
PCHCH3]; δC (100.6 MHz) 185.8 [d, 2J(P,C) 9.1, CO2], 96.4 [d,
2
δC (100.6 MHz) 106.5 [d, J(P,C) 2.0, CCH3 of C6Me6), 97.8
(s, CN), 68.0 (s, CH2OMe), 59.4 (s, CCH3 of CNBut), 58.4
1
(s, OCH3), 30.7 (s, CCH3 of CNBut), 28.0 [d, J(P,C) 24.1,
1
1
1
2J(P,C) 2.4, CCH3 of C6Me6), 56.8 (s, OCH3), 30.3 [d, J(P,C)
PCHCH3], 26.9 [d, J(P,C) 24.9, PCHCH3], 22.8 [d, J(P,C)
1
1
2
28.4, PCH2], 26.2 [d, J(P,C) 25.4, PCHCH3], 24.4 [d, J(P,C)
18.1, PCHCH3], 19.3 [d, 2J(P,C) 3.5, PCHCH3], 18.7 [d, 2J(P,C)
1.6, PCHCH3], 18.0 [d, 2J(P,C) 1.7, PCHCH3], 17.1 [d, 2J(P,C)
5.7, PCHCH3], 16.4 (s, CCH3 of C6Me6); δP (162.0 MHz) 60.5
(s, PPri2), Ϫ144.4 [sept, 1J(P,F) 710.6, PF6Ϫ].
25.3, PCH2], 19.6, 19.2 (both s, PCHCH3), 18.9 [d, J(P,C)
2.8, PCHCH3], 16.3 (s, CCH3 of C6Me6), 16.0 (s, PCHCH3);
1
δP (162.0 MHz) 43.1 (s, PPri2), Ϫ144.4 [sept, J(P,F) 712.8,
PF6Ϫ].
[Ru(ꢀ6-mes)(ꢁP-Pri2PCH2CH2OMe)(NCMe)Cl]PF6 15.
A
[Ru(ꢀ6-mes)(ꢁP-Pri2PCH2CH2OMe)(CO)Cl]PF6 11. Passing
a slow stream of CO for 10 min through a solution of 7 (48 mg,
0.08 mmol) in acetone (20 cm3) led to a quick change of color
from orange to yellow. After the solution was stirred for 30 min
under a CO atmosphere, the solvent was evaporated in vacuo.
The remaining light yellow solid was washed twice with ether
(5 cm3) and dried: yield 46 mg (91%), mp 107 ЊC (decomp.)
(Found: C, 37.70; H, 5.71. C19H33ClF6O2P2Ru requires C, 37.66;
solution of 7 (50 mg, 0.09 mmol) in CH2Cl2 (5 cm3) was treated
with acetonitrile (0.1 cm3) and stirred for 5 min at room
temperature. The solvent was evaporated in vacuo, the
remaining orange solid washed twice with ether (5 cm3) and
dried. The IR and NMR spectra revealed that a mixture of
the starting material and the product was obtained. Data
for 15: IR (KBr): ν(C᎐N) 2260 cmϪ1. NMR (CDCl3): δH (400
᎐
᎐
MHz) 5.67 (s, C6H3), 3.45 (m, CH2OMe), 3.32 (s, OCH3),
2.44, 2.12 (both m, PCHCH3), 2.36 (m, PCH2), 2.30 (s, CH3
H, 5.49%). Λ 78 cm2 ΩϪ1 molϪ1. IR (KBr): ν(CO) 1974 cmϪ1
.
NMR (CDCl3): δH (200 MHz) 6.78 (3 H, s, C6H3), 4.22 (3 H, s,
OCH3), 4.07 (2 H, m, CH2OMe), 2.82 (2 H, m, PCH2), 2.42,
2.20 (1 H each, both m, PCHCH3), 2.26 (9 H, s, CH3 of mes),
1.45, 1.40, 1.39, 1.36 (3 H each, all m, PCHCH3); δP (81.0 MHz)
63.9 (s, PPri2), Ϫ143.8 [sept, 1J(P,F) 712.2, PF6Ϫ].
of mes), 2.20 (s, CH3CN), 1.32, 1.27, 1.25, 1.02 (all m,
1
PCHCH3); δP (81.0 MHz) 40.6 (s, PPri2), Ϫ144.1 [sept, J(P,F)
712.8, PF6Ϫ].
[Ru(ꢀ6-C6Me6)(ꢁP-Pri2PCH2CH2OMe)(NCMe)Cl]PF6 16.
This compound was prepared as described for 15 from 8
(45 mg, 0.07 mmol) and acetonitrile (0.1 cm3) in CH2Cl2
(5 cm3). Orange solid consisting of a mixture of 8 and 16. Data
[Ru(ꢀ6-C6Me6)(ꢁP-Pri2PCH2CH2OMe)(CO)Cl]PF6 12. This
compound was prepared as described for 11 from 8 (110 mg,
0.18 mmol) and CO in acetone (10 cm3). Orange solid: yield
103 mg (90%), mp 95 ЊC (decomp.) (Found: C, 40.31; H, 5.86.
for 16: IR (KBr): ν(C᎐N) 2264 cmϪ1. NMR (CDCl3): δH (400
᎐
᎐
MHz) 3.38 (m, CH2OMe), 3.20 (s, OCH3), 2.71, 2.47 (both m,
D a l t o n T r a n s . , 2 0 0 3 , 4 4 1 – 4 4 8
445

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PCHCH3), 2.29 (m, PCH2), 2.15 (s, CH3CN), 2.10 (s, CH3 of
C6Me6), 1.24, 1.22, 1.08 (all m, PCHCH3); δP (81.0 MHz) 36.5
(s, PPri2), Ϫ142.9 [sept, 1J(P,F) 707.0, PF6Ϫ].
[Ru(ꢀ6-C6Me6)(ꢁ2P,C-Pri2PCHCO2Me)Cl] 20 and [Ru(ꢀ6-C6-
Me ){ꢁ2P,O-Pri PCH C(᎐O)O}Cl] 22. A solution of 6 (500 mg,
᎐
6
2
2
0.95 mmol) in THF (20 cm3) was treated first with Al2O3 (200
mg) and then five times with 10 mg portions of NaH (50 mg,
2.08 mmol). After the reaction mixture was stirred for 45 min at
room temperature, the solution was decanted and the residue
extracted twice with THF (10 cm3). The solution and the
extracts were combined and the solvent was evaporated in
vacuo. The residue was extracted with benzene (15 cm3), the
extract was concentrated to ca. 1 cm3 in vacuo, and the solution
was chromatographed on Al2O3 (basic, activity grade III). With
benzene/CH2Cl2 (3 : 1) a yellow fraction was eluted, which con-
tained compound 20: yield 28 mg (6%). With acetone, a second
yellow fraction was eluted which was brought to dryness in
vacuo. The remaining light yellow solid 22 was washed with
ether (5 cm3) and dried: yield 350 mg (78%).
[Ru(ꢀ6-C Me )(ꢁ2O,O-O C᎐O)(ꢁP-Pri PCH CH OMe)] 17.
᎐
6
6
2
2
2
2
A solution of 8 (102 mg, 0.16 mmol) in acetone (25 cm3) was
treated with a saturated solution of Na2CO3 in water (1 cm3)
and irradiated for 30 min at room temperature in an ultrasound
bath. The reaction mixture was filtered with Celite, and the
filtrate was brought to dryness in vacuo. The residue was
washed three times with ether (5 cm3) and then extracted with a
1 : 1 mixture of CH2Cl2 and hexane (30 cm3). The solvent from
the extract was evaporated and the remaining light yellow solid
dried in vacuo: yield 55 mg (67%), mp 142 ЊC (decomp.) (Found:
C, 52.58; H, 7.62. C22H39O4PRu requires C, 52.89; H, 7.87%).
IR (CH Cl ): ν(C᎐O) 1659 cmϪ1. NMR (CDCl3): δH (400 MHz)
᎐
2
2
3.59 (2 H, m, CH2OMe), 3.34 (3 H, s, OCH3), 2.23 (2 H, m,
PCH2), 2.13 (2 H, m, PCHCH3), 2.09 (18 H, s, CH3 of C6Me6),
Data for 20: mp 120 ЊC (decomp.) (Found: C, 51.42; H, 7.41.
C21H36ClO2PRu requires C, 51.69; H, 7.44%). IR (CH2Cl2):
3
3
1.14 [6 H, dd, J(P,H) 14.2, J(H,H) 7.1, PCHCH3], 1.11 [6 H,
dd, 3J(P,H) 14.9, 3J(H,H) 7.1, PCHCH3]; δC (100.6 MHz) 166.3
(s, CO3), 95.0 [d, 2J(P,C) 2.7, CCH3 of C6Me6), 65.8 (s,
ν(C᎐O) 1668 cmϪ1. NMR (C6D6): δH (400 MHz) 3.56 (3 H, s,
᎐
OCH3), 2.64 [1 H, 2J(P,H) 4.1, PCHCO2], 2.39, 2.33 (1 H each,
4
both m, PCHCH3), 1.89 [18 H, d, J(P,H) 0.9, CH3 of C6Me6],
1
CH2OMe), 58.4 (s, OCH3), 28.3 [d, J(P,C) 21.6, PCHCH3],
1.31, 1.28 (3 H each, m, PCHCH3), 1.23 [3 H, dd, 3J(P,H) 15.9,
3J(H,H) 7.3, PCHCH3], 1.13 [3 H, dd, 3J(P,H) 18.1, 3J(H,H) 7.6,
PCHCH3]; δP (81.0 MHz) 29.1 (s).
20.2 [d, 1J(P,C) 26.0, PCH2], 18.4, 15.2 (both s, PCHCH3), 15.9
(s, CCH3 of C6Me6); δP (162.0 MHz) 37.3 (s).
Data for 22: mp 202 ЊC (Found: C, 50.44; H, 6.99. C20H34-
[Ru(ꢀ6-mes){ꢁ2P,O-Pri PCH᎐C(O)OMe}Cl] 18. A solution
ClO PRu requires C, 50.68; H, 7.23%). IR (KBr): ν(C᎐O) 1631
᎐
᎐
2
2
of 9 (101 mg, 0.17 mmol) in THF (15 cm3) was treated with a
suspension of KOBut (19 mg, 0.17 mmol) in THF (5 cm3) and
stirred for 15 min at room temperature. After the solvent was
evaporated in vacuo, the residue was extracted with a 3 : 1 mix-
ture of hexane/CH2Cl2 (10 cm3). The extract was brought to
dryness in vacuo, the remaining light red solid washed with
small portions of hexane (0 ЊC) and dried: yield 59 mg (78%),
mp 85 ЊC (decomp.) (Found: C, 48.07; H, 7.11. C18H30ClO2PRu
requires C, 48.48; H, 6.78%). IR (KBr): ν(C᎐O)/ν(C᎐C) 1524
cmϪ1. NMR (CDCl3): δH (400 MHz) 2.84 [1 H, dd, 2J(P,H) 10.0,
2J(H,H) 16.0, PCH2], 2.73, 2.43 (1 H each, both m, PCHCH3),
2.30 [1 H, dd, 2J(P,H) 10.3, 2J(H,H) 16.0, PCH2], 2.07 [18 H, d,
4J(P,H) 0.6, CH3 of C6Me6], 1.26 [3 H, dd, 3J(P,H) 16.0, 3J(H,H)
7.4, PCHCH3], 1.23 [3 H, dd, 3J(P,H) 12.2, 3J(H,H) 7.1,
PCHCH3], 1.18 [3 H, dd, 3J(P,H) 13.5, 3J(H,H) 7.4, PCHCH3],
3
3
1.15 [3 H, dd, J(P,H) 15.2, J(H,H) 7.2, PCHCH3]; δC (100.6
MHz) 179.7 [d, 2J(P,C) 8.5, CO2], 95.1 [d, 2J(P,C) 2.8, CCH3 of
C6Me6], 29.6 [d, 1J(P,C) 29.1, PCH2], 25.9 [d, 1J(P,C)
24.3, PCHCH3], 24.4 [d, 1J(P,C) 19.1, PCHCH3], 19.3 [d,
2J(P,C) 4.8, PCHCH3], 18.6 [d, 2J(P,C) 1.7, PCHCH3], 18.3 [d,
᎐
᎐
cmϪ1. NMR (C6D6): δH (200 MHz) 4.39 (3 H, s, C6H3), 3.55 (3
H, s, OCH3), 3.19 [1 H, 2J(P,H) 3.7, PCHCO2], 2.49, 2.01 (1 H
each, both m, PCHCH3), 1.79 (9 H, s, CH3 of mes), 1.27 [3 H,
dd, 3J(P,H) 16.0, 3J(H,H) 7.7, PCHCH3], 1.23 [3 H, dd, 3J(P,H)
13.5, 3J(H,H) 7.5, PCHCH3], 1.03 [3 H, dd, 3J(P,H) 12.1,
3J(H,H) 6.9, PCHCH3], 1.02 [3 H, dd, 3J(P,H) 15.5, 3J(H,H) 6.9,
2
2J(P,C) 2.7, PCHCH3], 17.6 [d, J(P,C) 5.9, PCHCH3], 16.2 (s,
CCH3 of C6Me6); δP (162.0 MHz) 45.8 (s); MS (EI): m/z 474
(Mϩ, 28.8%).
2
PCHCH3]; δC (100.6 MHz) 180.5 [d, J(P,C) 28.6, CO2], 102.1
[Ru(ꢀ6-mes){ꢁ2P,O-Pri PCH C(᎐O)O}Cl] 21. This com-
᎐
2
2
[d, 2J(P,C) 1.9, CCH3 of mes], 81.1 [d, 2J(P,C) 3.8, CH of mes],
53.1 (s, OCH3), 44.5 [d, 1J(P,C) 70.6, PCHCO2], 26.6 [d, 1J(P,C)
22.9, PCHCH3], 26.5 [d, 1J(P,C) 35.3, PCHCH3], 20.2 [d,
2J(P,C) 3.8, PCHCH3], 19.9 [d, 2J(P,C) 4.8, PCHCH3], 19.5 [d,
pound was prepared as described for 22 from 5 (107 mg, 0.22
mmol), Al2O3 (200 mg) and NaH (50 mg, 2.08 mmol) in THF
(30 cm3). After the by-product 19 was separated by column
chromatography (yield 15 mg; 15%), a light yellow solid was
isolated: yield 76 mg (80%); mp 198 ЊC (Found: C, 47.56; H,
6.54; Ru, 23.62. C17H28ClO2PRu requires C, 47.28; H, 6.53; Ru,
2
2J(P,C) 1.9, PCHCH3], 19.0 (s, CCH3 of mes), 18.8 [d, J(P,C)
5.7, PCHCH3]; δP (81.0 MHz) 55.0 (s); MS (EI): m/z 446 (Mϩ,
62.0%).
23.40%). IR (KBr): ν(C᎐O) 1632 cmϪ1. NMR (CDCl3): δH (400
᎐
2
MHz) 4.92 (3 H, s, C6H3), 2.80 [1 H, dd, J(P,H) 9.9, J(H,H)
[Ru(ꢀ6-mes)(ꢁ2P,C-Pri2PCHCO2Me)Cl] 19. A solution of 18
(80 mg, 0.18 mmol) in benzene (5 cm3) was stirred for 3 d at
room temperature. The solution was concentrated to ca. 1 cm3
in vacuo and hexane (10 cm3) was added. A yellow solid precipi-
tated which was filtered, washed with small portions of hexane
(0 ЊC) and dried: yield 70 mg (88%), mp 174 ЊC (Found: C,
48.10; H, 6.75. C18H30ClO2PRu requires C, 48.48; H, 6.78%). IR
16.1, PCH2], 2.65, 2.39 (1 H each, both m, PCHCH3), 2.24 [1 H,
dd, 2J(P,H) 10.4, 2J(H,H) 16.1, PCH2], 2.11 (9 H, s, CH3 of mes),
3
3
1.23 [3 H, dd, J(P,H) 16.4, J(H,H) 7.4, PCHCH3], 1.20 [3 H,
dd, 3J(P,H) 15.5, 3J(H,H) 7.2, PCHCH3], 1.17 [3 H, dd, 3J(P,H)
14.3, 3J(H,H) 7.7, PCHCH3], 1.15 [3 H, dd, 3J(P,H) 13.0,
3J(H,H) 7.0, PCHCH3]; δP (162.0 MHz) 50.0 (s).
(KBr): ν(C᎐O) 1661 cmϪ1. NMR (C6D6): δH (400 MHz) 4.48
Reaction of compound 18 with water
᎐
2
(3 H, s, C6H3), 3.57 (3 H, s, OCH3), 2.71 [1 H, J(P,H) 3.1,
A solution of 18 (94 mg, 0.21 mmol) in acetone (10 cm3) was
treated with water (0.1 cm3) and stirred for 10 min at room
temperature. After the solvent was evaporated in vacuo, the
remaining light yellow solid was washed three times with ether
(5 cm3) and dried: yield 86 mg (95%). The product was identi-
fied as 21 by comparison with the spectroscopic data of an
authentic sample.
PCHCO2], 2.46, 2.36 (1 H each, both m, PCHCH3), 1.93 (9 H, s,
CH3 of mes), 1.32 [3 H, dd, 3J(P,H) 17.9, 3J(H,H) 7.2,
PCHCH3], 1.27 [3 H, dd, 3J(P,H) 16.5, 3J(H,H) 7.4, PCHCH3],
3
3
1.23 [3 H, dd, J(P,H) 12.8, J(H,H) 6.8, PCHCH3], 1.11 [3 H,
3
3
dd, J(P,H) 18.1, J(H,H) 7.6, PCHCH3]; δC (50.3 MHz) 179.5
2
2
[d, J(P,C) 1.6, CO2], 101.3 (s, CCH3 of mes), 81.3 [d, J(P,C)
3.5, CH of mes], 50.3 (s, OCH3), 26.2 [d, 1J(P,C) 20.2,
PCHCH3], 21.5 [d, 1J(P,C) 18.0, PCHCH3], 21.5, 21.0, 20.8 (all
s, PCHCH3), 19.5 (s, CCH3 of mes), 18.7 [d, 2J(P,C) 4.8,
PCHCH3], 10.0 (s, PCHCO2); δP (162.0 MHz) 31.3 (s); MS
(EI): m/z 446 (Mϩ, 100%).
Reaction of compound 18 with HCl
A slow stream of dry HCl was passed through a solution of 18
(54 mg, 0.12 mmol) in benzene (15 cm3) for ca. 20 s at room
D a l t o n T r a n s . , 2 0 0 3 , 4 4 1 – 4 4 8
446

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Table 3 Crystallographic data for 19 and 25
19
25
Formula
M
Crystal system
Space group
a/Å
b/Å
c/Å
C18H30ClO2PRu
445.91
Monoclinic
P21/n (no. 14)
9.195(3)
15.398(3)
14.193(5)
94.69(2)
2002.7(10)
293(2)
C32H40ClO3PRu
640.13
Monoclinic
P21/n (no. 14)
12.472(8)
14.435(7)
17.992(11)
104.81(3)
3132(3)
β/Њ
V/Å3
T /K
293(2)
Z
4
4
Dc/g cmϪ3
λ(Mo-Kα)/Å
µ/mmϪ1
1.479
0.71073
0.991
1.358
0.71073
0.667
No. of reflections measured
3117
5126
No. of unique reflections
3117 [R(int) = 0.0000]
0.0178
0.0726
0.245/Ϫ0.212
4880 [R(int) = 0.0677]
0.0483
0.1155
0.342/Ϫ0.491
R1a
wR2b
Residual electron density/e ÅϪ3
2
½
2
a R = Σ|Fo Ϫ Fc/ΣFo [for Fo > 2σ(Fo)] for the number of observed reflections [I > 2σ(I )], respectively. b wR2 = [Σw(Fo2 Ϫ Fc2)2/Σw(Fo )2] ; wϪ1 = [σ2(Fo )
ϩ (0.400P)2 ϩ 0.4395P] 19, wϪ1 = [σ2(Fo ) ϩ (0.0476P)2 ϩ0.0000P] 25, where P = (Fo2 ϩ 2Fc2)/3; for all data reflections, respectively.
2
temperature. The solution was stirred for 10 min and then the
solvent was evaporated in vacuo. The remaining orange solid
was identified as 5 by comparison with the spectroscopic data
of an authentic sample. Yield quantitative.
3J(H,H) 7.1, PCHCH3], 0.95 [3 H, dd, 3J(P,H) 15.8, 3J(H,H) 7.0,
PCHCH3]; δC (100.6 MHz) 191.0 (s, CO2), 181.6 [d, J(P,C)
2
27.5, C(O)CHPh2], 143.4, 142.9, 129.8, 129.7, 129.1, 128.5,
2
126.1, 125.8 (all s, C6H5), 102.3 [d, J(P,C) 1.9, CCH3 of mes],
1
2
83.2 [d, J(P,C) 59.4, PC᎐C], 80.1 [d, J(P,C) 3.4, CH of mes],
᎐
3
1
[Ru(ꢀ6-mes){ꢁ2P,O-Pri PC(C(᎐O)NHPh)᎐C(O)OMe}Cl] 24.
60.9 [d, J(P,C) 3.8, CHPh2], 53.2 (s, OCH3), 32.2 [d, J(P,C)
29.0, PCHCH3], 23.9 [d, 1J(P,C) 36.1, PCHCH3], 19.7 [d,
2J(P,C) 1.5, PCHCH3], 19.2 [d, 2J(P,C) 2.0, PCHCH3], 19.0 [d,
2J(P,C) 3.2, PCHCH3], 18.8 (s, PCHCH3), 17.6 (s, CCH3 of
mes); δP (162.0 MHz) 79.0 (s).
᎐
᎐
2
A solution of 18 (74 mg, 0.17 mmol) in benzene (10 cm3) was
treated with PhNCO (27 mg, 0.23 mmol) and stirred for 2 h at
room temperature. The solvent was evaporated in vacuo and the
orange residue was washed three times with hexane (5 cm3). The
1H and 31P NMR data revealed that the remaining solid con-
sisted mainly of 24 (ca. 85%). Attempts to separate 24 from the
un-identified by-products by chromatographic techniques or
fractional crystallization failed. Data for 24: IR (KBr): ν(NH)
3390, ν(C᎐O) 1630, ν(C᎐O)/ν(C᎐C) 1589 cmϪ1. NMR (C6D6):
Crystallography
Single crystals of both, 19 and 25, were grown from a saturated
solution in hexane which was slowly cooled from 60 ЊC to room
temperature. Crystal data collection parameters are summar-
ized in Table 3. Intensity data were corrected for Lorentz and
polarization effects. Empirical absorption corrections (ψ-scan
method, minimal transmission 91.30 and 84.19%, respectively)
were applied. Data reduction was performed with Enraf-
Nonius CAD4 software. The structures were solved by direct
methods (SHELXS-97).19 Atomic coordinates and anisotropic
thermal displacement parameters of the non-hydrogen atoms
were refined anisotropically by full-matrix least squares on F 2
(SHELXL-97).20 The positions of all hydrogen atoms were
calculated according to idealised geometries and were refined
by using the riding method.
᎐
᎐
᎐
δH (400 MHz) 9.01 (1 H, s, NH), 7.82–6.46 (5 H, m, C6H5),
4.48 (3 H, s, C6H3), 3.58 (3 H, s, OCH3), 2.42, 2.35 (1 H each,
both m, PCHCH3), 1.92 (9 H, s, CH3 of mes), 1.32, 1.02 (3 H
each, both m, PCHCH3), 0.85 (6 H, m, PCHCH3); δC (100.6
2
MHz) 176.5 [d, J(P,C) 28.0, CO2], 167.2 (s, CNHPh), 139.2,
132.0, 127.4, 119.3 (all s, C6H5), 100.9 [d, 2J(P,C) 1.5, CCH3 of
2
1
mes], 72.1 [d, J(P,C) 2.2, CH of mes], 70.8 [d, J(P,C) 62.2,
PC᎐C], 55.4 (s, OCH ), 29.3 [d, 1J(P,C) 28.9, PCHCH ], 27.0 [d,
᎐
3
3
1J(P,C) 33.2, PCHCH3], 19.5 [d, 2J(P,C) 3.2, PCHCH3], 19.2 [d,
2J(P,C) 2.4, PCHCH3], 18.7 [d, J(P,C) 5.0, PCHCH3], 18.2 (s,
2
CCH3 of mes), 18.0, 17.4 (both s, PCHCH3); δP (162.0 MHz)
64.6 (s).
CCDC reference numbers 123242 (19) and 193365 (25).
See http://www.rsc.org/suppdata/dt/b2/b208891f/ for crystal-
lographic data for 25 in CIF or other electronic format.
[Ru(ꢀ6-mes){ꢁ2P,O-Pri PC(CO Me)᎐C(O)CHPh }Cl] 25. A
᎐
2
2
2
solution of 18 (187 mg, 0.42 mmol) in a 3 : 1 mixture of hexane/
CH2Cl2 (10 cm3) was treated with Ph2CCO (175 mg, 0.90 mmol)
and stirred for 1 h at room temperature. The solvent was evap-
orated in vacuo, the residue was washed twice with hexane
(5 cm3) and then dissolved in benzene (1 cm3). The solution was
chromatographed on Al2O3 (basic, activity grade III). With
benzene, an orange fraction was eluted, which was brought to
dryness in vacuo. The remaining orange solid was washed three
times with hexane (5 cm3) and dried: yield 180 mg (67%); mp
112 ЊC (decomp.) (Found: C, 59.72; H, 6.02. C32H40ClO3PRu
Acknowledgements
We gratefully acknowledge financial support from the Deutsche
Forschungsgemeinschaft (SFB 347), the Fonds der Chemischen
Industrie and BASF AG. We also thank Mrs R. Schedl and
Mr C. P. Kneis (DTA and elemental analyses), Dr G. Lange
and Mr F. Dadrich (mass spectra), and Mrs M.-L. Schäfer and
Dr W. Buchner (NMR spectra).
requires C, 60.04; H, 6.30%). IR (KBr): ν(C᎐O) 1677, ν(C᎐O)/
᎐
᎐
ν(C᎐C) 1610 cmϪ1. NMR (C6D6): δH (400 MHz) 7.89, 7.38,
᎐
References
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D a l t o n T r a n s . , 2 0 0 3 , 4 4 1 – 4 4 8
448