Chromium, iron, ruthenium and gold complexes of 3,3-(biphenyl-2,2′-diyl)-1-diphenylphosphino-1-phenylallene: A versatile ligand

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Journal of Organometallic Chemistry 693 (2008) 1759–1770

www.elsevier.com/locate/jorganchem

Chromium, iron, ruthenium and gold complexes

of 3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphosphino-1-phenylallene:

A versatile ligand

Emilie V. Banide ^a, John P. Grealis ^a, Helge Muller-Bunz ^a, Yannick Ortin ^a, Michael Casey ^a,

¨

Claudio Mendicute-Fierro ^b, M. Cristina Lagunas ^b,*, Michael J. McGlinchey ^a,*

^aSchool of Chemistry and Chemical Biology, University College Dublin, Belﬁeld, Dublin 4, Ireland

^bSchool of Chemistry and Chemical Engineering, Queen’s University Belfast, Belfast BT9 5AG, U.K.

Received 4 November 2007; received in revised form 5 January 2008; accepted 6 January 2008

Available online 7 February 2008

Abstract

Successive treatment of 9-(phenylethynyl)ﬂuoren-9-ol (1a), with HBr, butyllithium and chlorodiphenylphosphine furnishes 3,3-(biphe-

nyl-2,2⁰-diyl)-1-diphenylphosphino-1-phenylallene (5). Moreover, reaction of 1a directly with chlorodiphenylphosphine yields the corre-

sponding allenylphosphine oxide (6). The allenylphosphine (5), and Fe₂(CO)₉initially form the phosphine–Fe(CO)₄complex, 11, which

is very thermally sensitive and readily loses a carbonyl ligand. In the resulting phosphine–Fe(CO)₃system, 12, the additional site at iron is

coordinated by the allene double bond adjacent to phosphorus; the Fe(CO)₃tripod in 12 exhibits restricted rotation on the NMR time-

scale even at room temperature. The corresponding chromium complex, (5)-Cr(CO)₅(9), has also been prepared. The gold complexes (5)-

AuCl (13), and [(5)-Au(THT)]⁺X^ꢀ, where (THT) is tetrahydrothiophene, and X = PF₆(14a), or ClO₄(14b), are analogous to the known

triphenylphosphine–gold complexes. In contrast, in the (arene)(allenylphosphine)RuCl₂system the allene double bond adjacent to phos-

phorus displaces a chloride, and the resulting cationic species undergoes nucleophilic attack by water yielding ultimately a ﬁve-membered

Ru–P–C@C–O ruthenacycle (17). Thus, the allenylphosphine (5), reacts initially as a conventional mono-phosphine but, when the metal

centre has a readily displaceable ligand such as a carbonyl or halide, the allene double bond adjacent to the phosphorus can also function

as a donor. X-ray crystal structures are reported for 5, 6, 11, 12, 13, 14a, 14b and 17.

Keywords: Allenyl-phosphines; Iron carbonyls; Ruthenium chloride; Gold

1. Introduction

and halogens. Since many tetracenes are known to be elec-

troluminescent [4], it was hoped that the introduction of a

wider range of functional groups into the precursor allenes

would allow greater control of their luminescent and other

photophysical or electro-conductive properties. We here

report the synthesis and characterization of 3,3-(biphenyl-

2,2⁰-diyl)-1-bromo-1-phenylallene (2a), and its conversion

to the novel ligand 3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphos-

phino-1-phenylallene (5); the corresponding phosphine

oxide (6), has also been prepared. Furthermore, the reac-

tions of the allenylphosphine (5) with chromium and iron

carbonyls, and also with gold and ruthenium chlorides,

are described.

In continuation of our studies on the syntheses and

dimerizations of ﬂuorenylidene-derived allenes to form

bis-alkylidenecyclobutanes, and ultimately tetracenes [1–

3], we wished to incorporate substituents containing other

main group elements, in particular phosphorus, silicon

*

Corresponding authors. Tel.: +353 1 716 2880; fax: +353 1 716 1178.

E-mail addresses: c.lagunas@qub.ac.uk (M. Cristina Lagunas),

michael.mcglinchey@ucd.ie (M.J. McGlinchey).

doi:10.1016/j.jorganchem.2008.01.046

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E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

2. Results and discussion

investigation of its reaction with a chlorophosphine with

a view to obtaining a novel ligand possessing several poten-

tial coordination sites.

The reaction of ﬂuorenone with lithio-alkynes yields,

after hydrolysis, the corresponding 9-alkynyl-ﬂuoren-9-

ols, where R = phenyl (1a), p-tolyl (1b), p-methoxyphenyl

(1c), or trimethylsilyl (1d). A general method for the con-

version of an alkynol into the corresponding alkyne

involves treatment with BF₃and triethylsilane [5]. Presum-

ably, the reaction proceeds via coordination of the hydro-

xyl group to boron, transfer of ﬂuoride from boron to

silicon, and delivery of a hydride from silicon to carbon,

possibly in a six-membered transition state. As shown in

Scheme 1, subsequent reaction with triethylamine brings

about eﬃcient isomerization from alkynes to allenes [6],

dimerization via a series of 1,2-dialkenylidene-cyclobutanes

and, ﬁnally, formation of two families of tetracenes [3].

However, this procedure for the conversion of alkynols

into alkynes fails when the R group possesses a substituent

with a lone pair to which the BF₃can coordinate, e.g. the

methoxy group in 1c; likewise, this route is inapplicable

for 1d since the trimethylsilyl substituent is susceptible to

attack by ﬂuoride. Consequently, we chose to treat the

alkynols, 1a–d, with HBr to generate bromoallenes, 2a–d;

conversion to the corresponding Grignard or organolith-

ium reagent and subsequent hydrolysis yielded the required

allenes, 3a–d, directly. The formation and dimerization of a

range of silyl- and halo-allenes has been described else-

where [7]. However, the ready accessibility of 3,3-(biphe-

nyl-2,2⁰-diyl)-1-lithio-1-phenylallene (4a) prompted the

When the bromoallene (2a) was treated successively with

n-butyllithium and chlorodiphenylphosphine, the novel

ligand

3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphosphino-1-

phenylallene (5), was isolated in 84% yield after chromato-

graphic separation; this allene does not dimerize. Interest-

ingly, when initially isolated as an oil, the product 5 is

purple, but after recrystallization from dichloromethane/

pentane it was obtained as pale yellow X-ray quality crys-

tals. The structure (Fig. 1) reveals that the allene double

bonds in 5 are not signiﬁcantly diﬀerent [C(9)@C(10)

˚

1.312(3) A; C(10)@C(11) 1.309(3) A], and the allenyl-car-

˚

bon–phosphorus distance is 1.853(3) A. This contrasts with

the situation in the precursor bromoallene (2a), in which

˚

the C(9)@C(10) bond [1.321(3) A] is signiﬁcantly longer

˚

than the C(10)@C(11) bond [1.292(3) A] [7].

Previously synthesized phosphinoallenes include

H₂C@C@CH–P(Ar)X, where X = Cl or NEt₂[8], H₂C@

C(Me)–P(Ar)R, where R = H, Cl, Me, TMS [9], and

PhCH@C@C(Ph)–PPh₂[10]. The phosphonium-allene

[Ph₂C@C@CH-P(cyclohexyl)₃]⁺[11], the bis(phospho-

nium)allenes [Ph₃P–CR@C@CR–PPh₃]²⁺, where R = NMe₂

or H [12,13], and a diphosphaisobenzene [14], have also

been reported.

By analogy to previously reported syntheses of phosphi-

noyl allenes [15], we have also prepared the phosphine-

oxide analogue of 5, i.e. 3,3-(biphenyl-2,2⁰-diyl)-1-diphenyl-

O

Ph₂P-O

Ph₂P

Ph

5

6

Ph

Ph₂PCl

Et₃N

-HCl

Br

R

Li

BuLi

Et₃N

HBr

Ph

4a

2a-d

HO

HOAc

H⁺/H₂O

H

R

BF₃

Et₃SiH

1a-d

H

0 ^oC

R

H

R

3a-d

(R=phenyl or tolyl)

R

H

40 ^oC

Ph

H

(R=Ph)

H

Ph

180 ^oC

+

Ph

Scheme 1. Syntheses and dimerizations of (biphenyl-2,2⁰-diyl)-allenes.

E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

1761

˚

1.318 (3) A] [17]. In other systems, the two double bonds

are of similar length [18,19].

C21

C20

C22

C28

Only a small number of organometallic derivatives of

allenylphosphines are known [11], and we are aware of only

a single example where a metal is coordinated directly to

the phosphorus [20]. In that case, a l-g¹:g²-allenyl di-iron

complex, 7, that possesses a bridging phosphido fragment,

rearranges (see Scheme 2) into the l-g¹:g³–allenylphos-

phine complex 8, in which both the allenyl linkage and

the phosphorus act as donors to iron.

Since allenylphosphine-organometallics with metal–

phosphine linkages appear not to have been extensively

explored, we chose to investigate the reactions of 5 with a

range of diﬀerent precursors, as indicated in Scheme 3.

Initially, 3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphosphino-1-

phenylallene (5), was allowed to react with (THF)Cr(CO)₅

and yielded the expected (allenylphosphine)Cr(CO)₅(9),

whose spectroscopic data corresponded well with those

previously reported for (Ph₃P)Cr(CO)₅(10) [21,22]. Thus,

¹³CO NMR resonances for 9 (10) are found at 221.2,

J_C–P= 5.7 Hz (221.7, J_C–P= 6 Hz) ppm [1 CO], and at

216.4, J_C–P= 12.8 Hz (216.9, J_C–P= 13 Hz) ppm [4

CO’s], the ³¹P NMR peak occurs at 63.0 (55.3) ppm, and

m_COabsorptions appear at 2063, 1982 and 1942 (2065,

1980 and 1940) cm^ꢀ1. These data indicate clearly the for-

mation of the (allenylphosphine)Cr(CO)₅(9). Thermolysis,

or treatment with trimethylamine-N-oxide, did not lead to

loss of a carbonyl ligand.

C29

C24

C19

C23

C27

C26

C6

C7

C8

C18

C5

C8A

C9

C25

P

C4B

C11

C12

C4A

C10

C4

C17

C9A

C1

C13

C16

C15

C3

C2

C14

Fig. 1. X-ray crystal structure of 3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphos-

phino-1-phenylallene (5). Thermal ellipsoids are drawn at the 15%

probability level.

phosphinoyl-1-phenylallene (6). The reaction of 9-phenyl-

ethynyl-9H-ﬂuoren-9-ol (1a), with chlorodiphenylphos-

phine proceeded with elimination of hydrogen chloride,

whereupon spontaneous migration of the phosphinoyl

moiety led directly to 6, whose structure is shown in

Fig. 2. As in the allenylphosphine (5), the allene double

bonds in 6 are not signiﬁcantly diﬀerent [C(9)@C(10)

˚

1.313(3) A; C(10)@C(11) 1.311(3) A], but the allenyl-car-

˚

bon–phosphorus distance is 1.8249(10) A, signiﬁcantly

Thus, the allenylphosphine (5), apparently behaves

toward (THF)Cr(CO)₅as does triphenylphosphine. Con-

versely, with iron carbonyl a diﬀerent type of reactivity

manifests itself. When 3,3-(biphenyl-2,2⁰-diyl)-1-diphenyl-

phosphino-1-phenylallene was allowed to react with

Fe₂(CO)₉in tetrahydrofuran at room temperature it

formed initially the yellow tetracarbonyliron complex 11,

the structure of which appears as Fig. 3. As with the

long-known (Ph₃P)Fe(CO)₄, the allenylphosphine complex

11 adopts a trigonal bipyramidal geometry in which the

phosphine is axial. The allene double bonds C(9)@C(10)

shorter than in 5. A search of the Cambridge Crystallo-

graphic Database revealed that structurally characterized

allenylphosphine oxides are rather rare. In H₂C@C@

C(Ph)P(@O)Ph₂, the H₂C@C double bond [1.316(5) A] is

longer than in the C@C–P linkage [1.290(5) A] [16],

whereas when the allenyl-bonded phenyl bears a tricarbon-

ylchromium group, as in Me₂C@C@C[Ph–Cr(CO)₃]P(@O)-

Ph₂, the situation is reversed [Me₂C@C 1.291(4) A; C@C–P

˚

and C(10)@C(11), 1.312(3) and 1.303(3) A, respectively,

are not signiﬁcantly diﬀerent, and the C(11)–P and P–Fe

linkages [1.844(3) and 2.2458(7) A, respectively] closely

parallel those found in (Ph₃P)Fe(CO)₄[23]. The allene moiety

is almost linear [C(9)–C(10)–C(11) is 178.4°], and the

C3

C2

˚

C15

C4

C1

C14

C13

C4A

C4B

C9A

C9

C16

C17

C11

C12

C5

C10

C8A

C8

O

Me

P

Me

C6

C23

C7

C

C24

C

C22

C18

H

C

C29

C27

C

C25

C26

C28

(OC)₃Fe

Ph₂P

(OC)₃Fe

Fe(CO)₃

PPh₂

C19

Fe(CO)₃

8

C21

C20

7

H

Fig. 2. X-ray crystal structure of 3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphos-

phinoyl-1-phenylallene (6). Thermal ellipsoids are drawn at the 25%

probability level.

Scheme 2. Rearrangement of a l-g¹:g²-allenyl complex into a l-g¹:g³-

allenylphosphine.

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E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

O

C

O

C

O

C

O

OC Fe

O

C

O

Fe

PPh₂

Ph

-CO

O

C

Ph

O

C

12

11

OC Cr

CO

C

O

Fe₂(CO)₉

THF

PPh₂

Ph

Cl

Au

9

PPh₂

Ph

(THF)Cr(CO)₅

PPh₂

Ph

(THT)AuCl

5

13

[(C₆H₅R)RuCl₂]₂

15

Ag⁺/THT

R

Cl

S

Ru

-

Ru

+

X

Au

Cl

O

H

PPh₂

Cl

PPh₂

Ph

PPh₂

Ph

17

16

14

(X = PF₆or ClO₄)

R=CH₂-NH-CO-C₆H₄-NO₂

Scheme 3. Reactions of 3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphosphino-1-phenylallene (5).

C15

C16

C28

C14

C17

C12

C27

C13

C25

C13

C10

C8

C26

O32

C7

C6

C12

C11

C25

O30

C1

C29

C8A

C30

O31

P

C5

C11

O30

C18

C24

C31

C32

C4B

C4A

C4

C9

C9A

C2

P

C3

C30

Fe

C9A

C4A

C33

O33

C10

C4

C9

C8A

C1

C18

C19

C32

C3

C2

C31

O31

C23

C22

C4B

C5

C19

C20

O32

C8

C7

C21

C6

Fig. 3. X-ray crystal structure of the allenylphosphine–Fe(CO)₄complex,

11. Thermal ellipsoids are drawn at the 25% probability level.

Fig. 4. X-ray crystal structure of the allenylphosphine–Fe(CO)₃complex,

12. Thermal ellipsoids are drawn at the 25% probability level.

C(10)–C(11)–P and C(11)–P–Fe angles are 119.9° and

115.2°, respectively.

However, the Fe(CO)₄complex, 11, is thermally very

sensitive and, even during the removal of solvent on a

rotary evaporator, readily loses carbon monoxide to pro-

duce red crystals of the corresponding Fe(CO)₃system,

12, in which the vacant site on iron is now occupied by

the adjacent double bond of the allene. As shown in

Fig. 4, the tricarbonyliron tripod in 12 is bonded in a

pseudo-allylic manner to two carbons and the phosphorus.

The allenyl moiety is no longer linear [C(9)–C(10)–C(11) is

138.6°], and the bonds C(9)@C(10) and C(10)@C(11) are

˚

1.357(3) and 1.425(3) A, respectively; the deviation of the

allene moiety from linearity is near the extreme of the

E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

1763

known range (ꢁ134–160°) for metal-bonded allenes, which

average ꢁ150° [24]. The Fe–C(10) and Fe–C(11) distances

diﬀerent metals. The reaction of 5 with (THT)AuCl

(THT = tetrahydrothiophene) parallels the behaviour of

triphenylphosphine. The initial reaction displaces the

weakly-bonded THT ligand to produce the (allenylphos-

phine)AuCl complex, 13, shown in Fig. 5. As with the tet-

racarbonyliron analogue, 11, the C(9)@C(10) and

˚

are markedly diﬀerent [1.971(3) and 2.185(2) A, respec-

˚

tively], the Fe–P [2.185(16) A] and P–C(11) [1.771(15) A]

bonds have shortened compared to those in 11, and, evi-

dently, the C(10)–C(11)–P and C(11)–P–Fe angles (102.5°

and 63.8°, respectively) have decreased as the iron leans

toward the C(10)@C(11) double bond. Finally, the three

carbonyl ligands adopt positions so as to place the iron

in an octahedral environment.

˚

C(10)@C(11) bond lengths [1.305(5) and 1.312(5) A,

respectively] are not signiﬁcantly diﬀerent; moreover, both

the allenyl and P–Au–Cl linkages are almost linear (175.0°

and 178.8°, respectively). When 13 was treated in situ with

a silver(I) salt to remove the chloride, the product reacted

with remaining THT to yield the [(allenylphos-

phine)gold(THT)]⁺cation, 14, that was crystallographi-

The ¹³C NMR spectrum of the (allenylphos-

phine)Fe(CO)₄complex 11 in the metal carbonyl region

shows only a single resonance, doublet split by phospho-

rus, thus paralleling the ﬂuxional behaviour previously

found in (Ph₃P)Fe(CO)₄[25]. In contrast, the tricarbonyl-

iron complex, 12, exhibits three ¹³CO resonances (each

exhibiting a diﬀerent coupling constant to phosphorus)

even at room temperature, and it is only as the temperature

is raised to ꢁ40 °C that line broadening becomes very evi-

ꢀ

cally characterized as both the PF₆and ClO₄salts, 14a

and 14b, respectively. The metric parameters for the two

salts are very similar, and Fig. 6 depicts the cation in the

hexaﬂuorophosphate case. Removal of THT before the

addition of the silver(I) salt to 13 resulted in extensive

decomposition to metallic gold. The elemental analysis of

14a is consistent with the proposed formula, but its ³¹P

NMR spectrum in CDCl₃solution shows, in addition to

the PF₆anion (septuplet at ꢀ142.9 ppm), two singlets at

45.4 and 37.3 ppm in a ca. 1:5 ratio, indicating the presence

of more than one species in solution. The signal at

37.3 ppm is broad at room temperature but sharp at

ꢀ60 °C. In addition, the THT ligand appears in the room

1

dent. However, the H and ¹³C resonances attributable to

the two non-equivalent benzo rings of the ﬂuorenylidene

moiety remain unchanged, as do those of the diastereotopic

phenyl groups on phosphorus, indicating that, although

rotation of the Fe(CO)₃tripod is an observable process,

the metal retains its attachment to one face of the allene

double bond, and racemization of the molecule does not

occur on the NMR time-scale. We are unaware of any pre-

vious reports of g³-bonded monometallic allenylphos-

phines of this type (although Doherty’s [20] di-iron

species 8 is somewhat related); however, we note the rele-

vance of Mathey’s observation of the equilibrium between

g³- and g¹-(phospha-allyl)[Fe(CO)Cp]W(CO)₅complexes

[26].

1

temperature H NMR spectrum of 14a as two broad sing-

lets centered at 3.41 and 2.11 ppm. At ꢀ60 °C, however,

four broad singlets corresponding to two sets of THT sig-

nals at ca. 1:10 ratio can be observed at 3.71 and 2.38 ppm,

and 3.46 and 2.10 ppm, respectively. This behaviour may

be attributed to the formation in solution of the symmetric

cations [(allenylphosphine)₂Au]⁺and [Au(THT)₂]⁺, in

equilibrium with the mixed species 14. The broadening of

the signals indicates ligand exchange on the NMR time

The allenylphosphine (5) also reacted with metal halides

and, once again, quite diverse behaviour was observed with

C15

C16

C17

C3

C2

C14

C26

C1

C9A

C27

C4

C12

C25

C4A

C4B

C13

C28

C11

C10

C9

C24

P

C23

C8A

C29

C5

C6

C22

C21

C8

Au

C18

C19

C7

Cl1

C20

Fig. 5. X-ray crystal structure of the allenylphosphine–gold chloride complex, 13. Thermal ellipsoids are drawn at the 70% probability level.

1764

E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

C15

C16

C17

C6

C7

C14

C8

C13

C33

C8A

C5

C4

C32

C31

C12

C11

C4B

C4A

C9

C10

C29

C9A

C1

S

P1

Au

C18

C30

C3

C2

C28

C27

C19

C24

C23

C22

C20

C21

C25

C26

Fig. 6. X-ray crystal structure of the allenylphosphine–gold-tetrahydrothiophene cation, 14a. Thermal ellipsoids are drawn at the 50% probability level.

1

scale. The H and ³¹P NMR spectra of 14b were obtained

only at room temperature but showed similar features to

those of 14a. Despite THT being a weakly coordinating

ligand, it can yield stable Au(I) species, although only a

few of them have been characterized by X-ray crystallogra-

phy [27,28]. The Au–S and Au–P distances in 14a

allenylphosphine (5), the anticipated phosphine complex,

16, was not detected. Instead an unexpected product, 17,

was identiﬁed crystallographically as the chelate complex

(arene)

, where R is 9-ﬂuorenyl.

The structure of 17 (see Fig. 7) reveals the presence of a

planar ﬁve-membered ruthenacycle in which the metal is

linked to a diphenylphosphino group and an oxygen

˚

[2.3321(13) and 2.2579(10) A, respectively] are comparable

to those observed in [Au(THT)(PPh₂C₆H₄NH₂ꢀ 2)]⁺

˚

(Ru–P = 2.3060(9), Ru–O = 2.075(2) A); the former cen-

˚

[2.321(2) and 2.261(2) A] [28]. The P–Au–S angle is almost

tral allene carbon, C(10), is now trigonal planar with a

linear in the latter [179.19(7)°] [28] but deviates slightly

from linearity in 14a [174.32(4)°]. The allenyl C@C bond

C(9)–C(10)–C(11) angle of 121.6°, and C(9)–C(10) and

˚

C(10)–C(11) distances of 1.512(4) A and 1.364(5) A,

respectively. In the solid state, intermolecular hydrogen

bonding between the chlorine and the amide hydrogen is

evident (Fig. 8).

˚

lengths [1.316(6) A and 1.307(5) A] and the C(9)–C(10)–

C(11) angle [175.9(4)°] in 14a are similar to those of 13.

As part of a bioorganometallic project involving the

linking of an organoruthenium moiety to a commercial

anticancer drug, the complex [(p-O₂N–C₆H₄–CO–NH–

CH₂– C₆H₅)RuCl₂]₂(15), was treated with a number of

ligands, such as DMSO, phosphines, etc., that cleave the

halogen bridges and yield the desired (arene)RuCl₂L sys-

tems. These results will be reported elsewhere [29]. How-

ever, when 15 was allowed to react with the

The formula of 17 corresponds to initial incorporation of

the allenylphosphine, addition of water, and loss of hydro-

gen chloride. As depicted in Scheme 4, one can readily envis-

age cleavage of the ruthenium dimer to form 16, followed by

coordination of the allene double bond adjacent to the phos-

phine with displacement of a chloride ion. The alkene linkage

C27

C18

C24

C15

P1

Ru1

O2

C12

C11

C36

Cl1

C37

C38

O4

C41

C10

C9

N2

N1

O1

C7

O3

C1

C6

C5

C4

C3

Fig. 7. X-ray structure of the allenylphosphine–ruthenium chelate complex, 17. Thermal ellipsoids are drawn at the 50% probability level.

E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

1765

C

H

O

P

Ru

Cl

N

Fig. 8. Intermolecular hydrogen bonding in the Ru chelate complex, 17.

R

+

Ru

Cl

+

OH₂

PPh₂

-

PPh₂

-Cl

H₂O

-

Ph

16

R

+

Ru

Cl

PPh₂

Ph

Cl

H

-H⁺

H

O

PPh₂

Ph

H

17

Scheme 4. Proposed mechanism for the formation of 17.

coordinated to the ruthenium(II) centre is now susceptible to

nucleophilic attack by water; successive proton migration,

coordination of oxygen to ruthenium and deprotonation

lead directly to the observed product 17. The most closely

related system of which we are aware was reported by Wer-

ner [30], whereby treatment of (mesitylene)RuCl₂(R₂P–

CH₂–CO₂Me) with AgPF₆, and then t-BuOK, yielded

(mesitylene)(Cl)Ru–PR₂–CH@C(OMe)–O, a chelate com-

plex directly analogous to 17.

To conclude, the allenylphosphine (5), reacts initially as a

conventional mono-phosphine but, when the metal centre

has a readily displaceable ligand such as a carbonyl or halide,

the allene double bond adjacent to the phosphorus can also

function as a donor. Moreover, when the alkene moiety is

coordinated to a positively charged metal center, it is ren-

dered susceptible to nucleophilic attack. In principle, the ﬂu-

orenyl fragment could also be a site for metal coordination

and work on this aspect is continuing.

1766

E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

3. Experimental

3.1. General methods

127.9 (d, J = 10.6 Hz, phenyl o-C), 127.6 (C₃, C₆), 126.8

(C₂, C₇), 122.8 (C₄, C₅), 111.2 (d, J = 23.6 Hz, C₁₁), 108.3

(d, J = 1.9 Hz, C₉); ³¹P {¹H} NMR (121 MHz, CDCl₃): d

ꢀ6.90; IR (liquid, CH₂Cl₂): 1916 cm^ꢀ1(C@C@C).

All reactions were carried out under an atmosphere of

dry nitrogen employing conventional benchtop and glove-

bag techniques. Merck silica gel 60 (230–400 mesh) was

3.3. Preparation of 3,3-(biphenyl-2,2⁰-diyl)-1-

diphenylphosphinoyl-1-phenylallene (6)

used for ﬂash chromatography. H and ¹³C NMR spectra

1

were recorded on Varian Inova 300 MHz, 400 MHz or

500 MHz spectrometers. Assignments were based on stan-

dard 2-dimensional NMR techniques (¹H–¹H COSY,

¹H–¹³C HSQC and HMBC, NOESY). Infrared spectra

were recorded on a Perkin–Elmer Paragon 1000 FT-IR

spectrometer and were calibrated with polystyrene. Melting

points were determined on an Electrothermal ENG instru-

ment and are uncorrected. Elemental analyses were carried

out by the Microanalytical Laboratory at University Col-

lege Dublin or at the Analytical Services and Environmen-

tal Projects (ASEP) Division at Queen’s University Belfast.

The alkynyl-ﬂuorenols 1a–1d were prepared as described

previously [7].

Triethylamine (89 lL, 0.64 mmol) was added to a solu-

tion of 9-phenylethynyl-9H-ﬂuoren-9-ol (1a), (150 mg,

0.53 mmol) in pentane (6 mL) and dichloromethane

(1 mL) at 0 °C. Chlorodiphenylphosphine (114.9 lL,

0.64 mmol) was then added and, after stirring for 1 h at

room temperature, the precipitate was ﬁltered oﬀ, washed

with water, and dried to give 3,3-(biphenyl-2,2⁰-diyl)-1-

diphenylphosphinoyl-1-phenyl-allene

(6)

(226 mg,

0.48 mmol; 91%) m.p. 193–195 °C as a white powder. Anal.

Calc. for C₃₃H₂₃OP ꢂ 0.5H₂O: C, 83.35; H, 5.09; P, 6.51.

Found: C, 83.62; H, 4.90; P, 6.84%. A sample suitable

for an X-ray crystal structure determination was obtained

by recrystallisation from dichloromethane/pentane. ¹H

NMR (500 MHz, CDCl₃): d 7.83 (d, 2H, J = 7.0 Hz, phe-

nyl o-H), 7.80 (d, 2H, J = 7.0 Hz, phenyl o-H), 7.75 (d,

2 H, J = 7.5 Hz, phenyl o-H), 7.64 (d, 2H, J = 7.5 Hz,

H₄, H₅), 7.48 (d, 2H, J = 7.5 Hz, H₁, H₈), 7.33 (t, 2H,

J = 7.5 Hz, H₃, H₆), 7.32–7.22 (m, 11H, H₂, H₇, phenyl

m-H, p-H); ¹³C NMR (125 MHz, CDCl₃) d 209.9 (d,

J = 4.5 Hz, C₁₀), 138.7 (C_4a, C_4b), 136.3 (d, J = 6.1 Hz,

C_8a, C_9a), 132.5 (phenyl ipso-C), 132.1 (d, J = 29.8 Hz, phe-

nyl ipso-C), 132.0 (d, J = 3.1 Hz, phenyl p-C), 131.6 (phe-

nyl o-C), 131.5 (phenyl o-C), 129.0 (phenyl m-C), 128.9

(d, J = 4.8 Hz, phenyl o-C), 128.6 (C₃, C₆), 128.4, 128.3

(phenyl m-C), 127.2 (d, J = 0.8 Hz, C₂, C₇), 123.2 (d,

J = 1.6 Hz, C₁, C₈), 120.3 (C₄, C₅), 109.8 (d, J = 94.4 Hz,

C₁₁), 109.4 (d, J = 13.0 Hz, C₉); ³¹P {¹H} NMR

(121 MHz, CDCl₃): d 30.08. IR (CHCl₃) 1921 cm^ꢀ1

(C@C@C).

3.2. Preparation of 3,3-(biphenyl-2,2⁰-diyl)-1-

diphenylphosphino-1-phenylallene (5)

To a solution of 3,3-(biphenyl-2,2⁰-diyl)-1-bromo-1-phe-

nyl-allene (2a), (500 mg, 1.45 mmol) in tetrahydrofuran

(15 mL), prepared as described previously [7], n-BuLi

(1.09 mL of a 1.6 M hexane solution, 1.74 mmol) was

added dropwise at ꢀ78 °C. After 30 min stirring, chlorodi-

phenylphosphine (340 lL, 1.89 mmol) in dichloromethane

(1 mL) was added dropwise. The solution was stirred at

ꢀ78 °C for 30 min, and at room temperature for 2 h,

quenched with water, and extracted with diethyl ether sev-

eral times. The organic layers were combined, washed with

brine, dried over MgSO₄, ﬁltered and concentrated to give

a yellow oil. Puriﬁcation of the crude product by chroma-

tography on silica gel using pentane/dichloromethane as

eluent gave 3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphosphino-

1-phenyl-allene (5), (551 mg, 1.22 mmol; 84%) as a purple

solid, m.p. 72–76 °C. Anal. Calc. for C₃₃H₂₃P0.25CH₂Cl₂:

C, 84.66; H, 5.02. Found: C, 84.36; H, 4.99%. A sample

suitable for an X-ray crystal structure determination was

obtained by recrystallisation from dichloromethane/pen-

tane. ¹H NMR (500 MHz, CDCl₃): d 7.74 (dt, 2H,

J = 1.5 Hz, J = 8.0 Hz, phenyl o-H), 7.66 (dd, 2H,

J = 1.0 Hz, J = 8.0 Hz, H₄, H₅), 7.52–7.47 (m, 4H, phenyl

o-H), 7.41 (d, 2H, J = 7.5 Hz, H₁, H₈), 7.32 (t, 2H,

J = 7.5 Hz, phenyl m-H), 7.29 (td, 2H, J = 1.0 Hz,

J = 7.5 Hz, H₃, H₆), 7.28 (td, 1H, J = 1.0 Hz, J = 7.5 Hz,

phenyl p-H), 7.21 (td, 2 H, J = 1.0 Hz, J = 7.5 Hz, H₂,

H₇), 7.14–7.11 (m, 6H, phenyl m-H, p-H); ¹³C NMR

(125 MHz, CDCl₃) d 206.8 (C₁₀), 138.28 (C_4a, C_4b), 137.5

(C_8a, C_9a), 135.4 (d, J = 10.8 Hz, phenyl ipso-C), 134.9

(d, J = 24.9 Hz, phenyl ipso-C), 133.9 (d, J = 19.6 Hz, phe-

nyl ipso-C), 129.1 (phenyl), 129.0 (phenyl m-C), 128.4 (phe-

nyl), 128.3 (phenyl), 128.2 (d, J = 1.3 Hz, phenyl p-C),

3.4. Preparation of (3,3-(biphenyl-2,2⁰-diyl)-1-

diphenylphosphino-1-phenylallene)Cr(CO)₅(9)

A solution of Cr(CO)₆(490 mg, 2.2 mmol) in dry tetra-

hydrofuran (300 mL) was photolysed in a quartz UV reac-

tor for 1 h, and added to

a

solution of the

allenylphosphine, 5, (1.0 g, 2.2 mmol) in tetrahydrofuran

(10 mL). The reaction was stirred overnight under nitro-

gen, concentrated, and triturated with dichloromethane.

The residues were ﬁltered oﬀ and the ﬁltrate crystallised

to give the (allenylphosphine)Cr(CO)₅complex, 9,

(683 mg, 1.06 mmol; 48%), m.p. 97–99 °C as a yellow pow-

der. Anal. Calc. for C₃₈H₂₃CrO₅P: C, 71.03; H, 3.61.

1

Found: C, 70.86; H, 3.74%. H NMR (400 MHz, CDCl₃):

d 7.85–7.26 (m), 7.72–7.62 (m), 7.57 (d, J = 7.6 Hz), 7.42–

7.20 (m); ¹³C NMR (100 MHz, CDCl₃): d 221.2 (d,

J = 5.7 Hz), 216.4 (d, J = 12.8 Hz), 206.8 (d, J = 1.8 Hz),

138.9, 136.8 (d, J = 3.8 Hz), 134.7 (d, J = 35.5 Hz), 133.8

(d, J = 13.0 Hz), 133.0 (d, J = 10.9 Hz), 130.6 (d,

E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

1767

J = 2.0 Hz), 129.5 (d, J = 3.8 Hz), 128.8, 128.6, 128.5,

127.4, 123.2, 120.5, 111.3 (d, J = 23.2 Hz), 109.2 (d,

J = 8.6 Hz); ³¹P {¹H} NMR (121 MHz, CDCl₃): d 63.0;

IR (solid, KBr): 2063 cm^ꢀ1, 1982 cm^ꢀ1, 1942 cm^ꢀ1(CO).

133.7 (d, J = 10.8 Hz), 133.7 (d, J = 10.8 Hz), (phenyl o-

C), 131.9 (d, J = 3.6 Hz, phenyl p-C), 131.9 (d,

J = 3.6 Hz, phenyl p-C), 129.0 (d, J = 9.1 Hz, phenyl m-

C), 129.0, 128.9 (d, J = 3.6 Hz), 128.6, 126.7 (phenyl C),

126.2 (C₇), 125.8 (C₂), 125.8 (C₆), 125.6 (d, J = 53.6 Hz,

phenyl ipso-C), 125.3 (d, J = 13.3 Hz, C₉), 124.8 (C₃),

124.0 (d, J = 57.8 Hz, phenyl ipso-C), 122.1 (C₁), 121.4

(C₈), 119.4 (C₅), 119.0 (C₄), 38.4 (d, J = 23.5 Hz, C₁₁);

³¹P {¹H} NMR (121 MHz, CDCl₃): d 12.48; IR (liquid,

CH₂Cl₂): 2040 cm^ꢀ1, 1979 cm^ꢀ1(C@O). Anal. Calc. for

C₃₆H₂₃FeO₃P0.25CH₂Cl₂: C, 71.19; H, 3.87; Fe, 9.13.

Found: C, 71.37; H, 3.93; Fe, 8.67%.

3.5. Preparation of (allenylphosphine)Fe(CO)₄(11) and

(allenylphosphine)Fe(CO)₃(12)

A solution of 3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphos-

phino-1-phenylallene (5), (290 mg, 0.64 mmol) in THF

and diiron nonacarbonyl (585 mg, 1.61 mmol) were stirred

for 48 h at room temperature, during which time the

Fe₂(CO)₉gradually went into solution. The solvent was

removed at low temperature and the crude material was

puriﬁed by chromatography on silica gel using pentane as

3.6. Preparation of (allenylphosphine)AuCl (13)

eluent.

[3,3-(Biphenyl-2,2⁰-diyl)-1-diphenylphosphino-1-

To [AuCl(THT)] [31] (35.6 mg, 0.11 mmol) dissolved in

dichloromethane (15 mL) was added the allenylphosphine,

5, (50 mg, 0.11 mmol). The solution was stirred for 2 h,

after which time the volume of the solution was reduced

in vacuo to ca. 2 mL. Addition of hexane to the dichloro-

methane solution yielded an oil that, upon removal of the

solvents in vacuo, solidiﬁed to give 13 (41 mg, 0.06 mmol;

54%) m.p. 212–213 °C. Anal. Calc. for C₃₃H₂₃

PAuCl0.25CH₂Cl₂: C, 56.71; H, 3.36. Found: C, 56.47;

H, 3.30%. A sample suitable for an X-ray crystal structure

determination was obtained by diﬀusion of hexane into a

dichloromethane solution of the product at ꢀ20 °C. ¹H

NMR (300 MHz, CDCl₃): d 7.75–7.60 (m, 8H, phenyl-

H), 7.44–7.19 (m, 15H, phenyl-H); ¹³C NMR (75 MHz,

CDCl₃): d 209.6 (C₁₀), 138.7 (C_4a, C_4b), 135.7 (d,

J = 5.7 Hz, C_8a, C_9a), 134.2, 134.0, 132.1, 132.1, 131.6 (d,

J = 11.5 Hz, phenyl ipso-C), 129.2, 129.1, 129.0, 128.9,

128.8, 128.1, 127.9, 127.2, 127.1, 123.1, 120.3, 110.9 (d,

J = 11.5 Hz, C₉), 106.7 (d, J = 52.8 Hz, C₁₁); ³¹P {¹H}

NMR (121 MHz, CDCl₃): d 31.3.

phenyl-allene]Fe(CO)₄(11), (215 mg, 0.35 mmol; 54%)

was isolated as a temperature-sensitive yellow solid. A sam-

ple suitable for an X-ray crystal structure determination

was obtained by recrystallisation from diethyl ether/pen-

tane. ¹H NMR (500 MHz, CDCl₃): d 7.79 (d, 2 H,

J = 8.0 Hz, phenyl o-H), 7.76 (d, 2H, J = 6.5 Hz, phenyl

o-H), 7.65 (d, 2H, J = 7.5 Hz, H₄, H₅), 7.56 (d, 2H,

J = 7.5 Hz, H₁, H₈), 7.38 (d, 2H, J = 8.0 Hz, phenyl o-

H), 7.36 (t, 3H, J = 7.5 Hz, H₃, H₆, phenyl p-H), 7.33–

7.27 (m, 10H, H₂, H₇, phenyl p-H, phenyl m-H); ¹³C

NMR (125 MHz, CDCl₃): d 213.5 (d, J = 18.8 Hz, CO),

207.9 (C₁₀), 138.4 (C_4a, C_4b), 136.5 (d, J = 5.00 Hz, C_8a,

C_9a), 133.2 (d, J = 10.5 Hz, phenyl o-C), 133.0 (d,

J = 11.9 Hz, phenyl ipso-C), 132.7 (d, J = 48.1 Hz, phenyl

ipso-C), 131.2 (d, J = 2.4 Hz, phenyl p-C), 129.6 (d,

J = 3.6 Hz, phenyl o-C), 128.9 (phenyl p-C), 128.6 (phenyl

m-C), 128.6 (d, J = 10.5 Hz, phenyl m-C), 128.5 (C₃, C₆),

127.2 (C₂, C₇), 123.1 (C₁, C₈), 120.3 (C₄, C₅), 110.4 (d,

J = 38.0 Hz, C₁₁), 108.3 (d, J = 10.0 Hz, C₉); ³¹P {¹H}

NMR (121 MHz, CDCl₃): d 79.77; IR (liquid, CHCl₃):

2050 cm^ꢀ1, 1977 cm^ꢀ1, 1940 cm^ꢀ1(C@O). A red solid,

3.7. Preparation of [(allenylphosphine)Au(THT)]PF₆

(14a)

identiﬁed

as

[3,3-(biphenyl-2,2⁰-diyl)-1-diphenylphos-

phino-1-phenylallene]Fe(CO)₃(12), (19 mg, 0.03 mmol;

5%), m.p. 203–206 °C, was also isolated, and a sample suit-

able for an X-ray crystal structure determination was

obtained by recrystallisation from dichloromethane/pen-

tane. It was subsequently shown that, upon gentle warm-

ing, 11 was converted quantitatively into 12. ¹H NMR

(500 MHz, CDCl₃): d 8.37 (d, 1H, J = 7.5 Hz, H₈), 7.78

(d, 1H, J = 7.5 Hz, H₅), 7.69 (d, 1H, J = 7.5 Hz, H₄),

7.67 (d, 1H, J = 7.5 Hz, phenyl-H), 7.65 (d, 1H,

J = 7.5 Hz, phenyl-H), 7.60–7.56 (m, 1H, phenyl-H),

7.49–7.43 (m, 1H, H₇, phenyl-H), 7.40–7.35 (m, 2H, H₆,

phenyl-H), 7.25 (td, 2H, J = 3.0 Hz, J = 7.5 Hz, phenyl-

H), 7.16–7.09 (m, 6H, H₃, phenyl-H), 7.07 (d, 1H,

To [AuCl(THT)] [31] (35.6 mg, 0.11 mmol) dissolved in

dichloromethane (15 mL) was added the allenylphosphine,

5, (50 mg, 0.11 mmol) and the solution was stirred for

30 min after which time AgPF₆(28.1 mg, 0.11 mmol) was

added. The solution was stirred for further 30 min, ﬁltered

through celite, and the resulting yellow solution was then

reduced in vacuo to ca. 2 mL. Addition of diethyl ether

produced a yellow precipitate (61.6 mg, 0.07 mmol; 68%)

m.p. 140–141 °C (turns purple on melting). A sample suit-

able for X-ray crystallography was obtained by diﬀusion of

1

hexane into a dichloromethane solution of 14a. H NMR

(300 MHz, CDCl₃): d 7.78–7.60 (m, 6H, phenyl-H), 7.56–

7.46 (m, 5H, phenyl-H), 7.44–7.28 (m, 12H, phenyl-H),

3.41 (s, brd, 4H, CH₂S), 2.11 (s, brd, 4H, CH₂); ³¹P {¹H}

NMR (121 MHz, CDCl₃) d 45.3 (s), 37.3 (s, brd), ꢀ142.9

(septuplet, J_PF= 714 Hz, PF₆). Anal. Calc. for

C₃₇H₃₁SP₂AuF₆0.25CH₂Cl₂: C, 49.61; H 3.52. Found: C,

49.68; H, 3.56%.

J = 8.0 Hz, H₁), 6.96 (td, 1H, J = 1.0 Hz,J = 7.5 Hz, H₂);

2

¹³C NMR (125 MHz, CDCl₃): d 211.7 (d, J_C–P

=

2

13.8 Hz, CO), 210.4 (d, J_C–P= 24.0 Hz, CO), 210.0 (d,

²J_C–P= 27.6 Hz, CO), 167.3 (d, J = 5.6 Hz, C₁₀), 140.0

(d, J = 3.5 Hz, C_8a), 139.6 (C_4b), 136.7 (d, J = 3.6 Hz,

C_9a), 136.7 (d, J = 2.6 Hz, phenyl ipso-C), 136.1 (C_4a),

Table 1

Crystallographic data

Compound

5

6

11

12

13

14a

14b

17

Empirical formula

f_w

C

450.48

₃₃H₂₃PO_0.096C₃₃H₂₃PO

C₃₇H₂₃O₄PFe C₃₆H₂₃O₃PFe C₃₄H₂₅PCl₃Au C₃₈H₃₃F₆P₂SCl₂Au

C₃₈H₃₃O₄PSCl₃Au

919.99 contains one

molecule of CH₂Cl₂

Triclinic

C₄₉H₄₀N₂O₄PCl₅Ru

1030.12 contains two

molecules of CH₂Cl₂

Triclinic

466.48

618.37

590.36

767.83

965.51 contains one

molecule of CH₂Cl₂

Triclinic

Crystal system

Space group

Monoclinic

P2₁/c (#14)

16.767(2)

13.1618(17)

11.3947(15)

90

95.061(2)

90

2504.8(6)

4

Monoclinic

C2/c (#15)

34.947(3)

9.3112(8)

15.8040(14)

90

100.035(2)

90

5063.9(8)

8

Triclinic

Monoclinic

P2₁/c (#14)

12.0591(13)

16.4153(17)

14.6403(16)

90

97.219(2)

90

2875.1(5)

4

ꢀ

P1 (#2)

˚

a (A)

8.6715(11)

12.5733(17)

14.3019(19)

94.560(2)

91.510(2)

97.881(2)

1538.6(4)

2

10.159(11)

10.767(11)

14.288(15)

75.101(17)

89.447(17)

77.311(17)

1472(3)

2

8.8805(10)

10.9889(12)

19.250(2)

93.885(2)

99.432(2)

98.917(2)

1822.3(4)

2

9.0214(7)

10.4304(8)

19.2422(15)

97.430(2)

98.163(2)

99.337(2)

1746.9(2)

2

15.8058(15)

17.9142(16)

18.4061(17)

79.981(2)

71.888(2)

68.567(2)

4593.1(7)

4

˚

b (A)

˚

c (A)

a (°)

b (°)

c (°)

3

˚

V (A )

Z

Density (calc.) (g cm^ꢀ3

Temp (K)

)

1.205

293(2)

1.224

293(2)

1.335

1.332

1.774

1.760

1.749

100(2)

1.490

100(2)

293(2)

100(2)

Absorption coeﬃcient

0.128

0.132

0.581

0.601

5.475

4.387

4.587

0.714

(mm^ꢀ1

)

F(000)

h Range (°)

952

50.00

1952

48

636

52.00

608

50.00

1496

56.00

948

60.00

908

58.00

2096

54.00

Index ranges

ꢀ19 6 h 6 19, ꢀ39 6 h 6 39, ꢀ10 6 h 6 10, ꢀ12 6 h 6 11, ꢀ15 6 h 6 15, ꢀ12 6 h 6 12,

ꢀ12 6 h 6 12,

ꢀ14 6 k 6 14,

ꢀ26 6 l 6 26

37660

9289 (0.0453)

450

ꢀ20 6 h 6 20,

ꢀ22 6 k 6 22,

ꢀ23 6 l 6 23

82323

20036 (0.0537)

1179

ꢀ15 6 k 6 15, ꢀ10 6 k 6 10, ꢀ15 6 k 6 15, ꢀ10 6 k 6 12, ꢀ21 6 k 6 21, ꢀ15 6 k 6 15,

ꢀ13 6 l 6 13

ꢀ18 6 l 6 17

ꢀ17 6 l 6 17

ꢀ16 6 l 6 16

ꢀ19 6 l 6 19

ꢀ27 6 l 6 27

38734

Reﬂections measured

Reﬂections used (R_int

Parameters

17574

15362

12003

10298

53693

)

4410 (0.0225) 3698 (0.0265) 5986 (0.0216) 5016 (0.0230) 6931 (0.0699)

317 316 388 370 353

10569 (0.0337)

451

Final R values I > 2r(I)]:

R₁, wR₂

0.0468, 0.1247 0.0468, 0.1211 0.0451, 0.1108 0.0385, 0.1005 0.0272, 0.0601 0.0403, 0.1034

0.0353, 0.0842

0.0473, 0.1151

R values (all data): R₁,

wR₂

0.0558, 0.1316 0.0558, 0.1277 0.0615, 0.1210 0.0439, 0.1047 0.0327, 0.0618 0.0443, 0.1061

0.0408, 0.0867

0.0766, 0.1310

Goodness-of-ﬁt on F²

Largest diﬀraction peak

1.064

1.030

1.023

1.020

1.083

1.104

1.063

1.819, ꢀ1.329

1.045

0.748, ꢀ0.744

0.312, ꢀ0.148 0.535, ꢀ0.217 0.596, ꢀ0.223 0.380, ꢀ0.194 1.289, ꢀ1.699 4.122 ꢀ1.633

ꢀ3

˚

and hole (e A

)

E.V. Banide et al. / Journal of Organometallic Chemistry 693 (2008) 1759–1770

1769

3.8. Preparation of [(allenylphosphine)Au(THT)]ClO₄

(14b)

C₁₆), 136.09 (d, J = 10 Hz, C₁₉/C₂₃or C₂₀/C₂₂), 137.84

(C₁₂), 139.35 (C₃₉), 139.92 (d, J = 47 Hz, C₁₈, C₂₄),

141.09 (C_4a), 141.93 (C_4b), 145.20 (C_9a), 146.25 (C_8a),

149.42 (C₄₂), 166.16 (C₃₈₎, 183.32 (d, J = 22 Hz, C₁₀); ³¹P

NMR (162 MHz, CDCl₃) d 61.89.

To [AuCl(THT)] [31] (35.6 mg, 0.11 mmol) dissolved in

dichloromethane (15 mL) was added the allenylphosphine

(5), (50 mg, 0.11 mmol) and the solution was stirred for

30 min after which time AgClO₄(23.0 mg, 0.11 mmol)

was added. The solution was stirred for further 30 min, ﬁl-

tered through celite, and the resulting yellow solution was

then reduced in vacuo to ca. 2 mL. Addition of diethyl

ether produced a white precipitate (56 mg, 0.06 mmol;

61%). A sample suitable for X-ray crystallography was

obtained by diﬀusion of pentane into a dichloromethane

solution of 14b. ¹H NMR (300 MHz, CDCl₃): d 7.78–

7.72 (m, 5H, phenyl-H), 7.64–7.48 (m, 6H, phenyl-H),

7.39–7.26 (m, 12H, phenyl-H), 3.48 (s, brd, 4H, CH₂S),

2.15 (s, brd, 4H, CH₂); ³¹P {¹H} NMR (121 MHz, CDCl₃)

d 45.2 (s), 36.8 (s, brd).

3.10. X-ray crystal structure determinations

Crystal data for 5, 6, 11, 12, 13, 14a, 14b and 17 were

collected using a Bruker SMART APEX CCD area detec-

tor diﬀractometer, and are listed in Table 1. A full sphere of

reciprocal space was scanned by phi-omega scans. Pseudo-

empirical absorption correction based on redundant reﬂec-

tions was performed by the program ^SADABS[32]. The struc-

tures were solved by direct methods using ^SHELXS-97 [33]

and reﬁned by full matrix least-squares on F²for all data

using ^SHELXL-97 [34]. Hydrogen atoms attached to nitrogen

were located in the diﬀerence Fourier map and allowed to

reﬁne freely with isotropic thermal displacement factors.

All other hydrogen atoms were added at calculated posi-

tions and reﬁned using a riding model. Their isotropic dis-

placement parameters were ﬁxed to 1.2 times the equivalent

isotropic displacement parameters of the carbon atom the

H-atom is attached to. Anisotropic temperature factors

were used for all non-hydrogen atoms.

3.9. Preparation of (arene)RuCl[Ph₂P–C(Ph)@CR–O]

(17)

To a solution of dichloro (N-benzyl-4-nitro-benzam-

ide)ruthenium(II) dimer (60 mg, 0.07 mmol) [29] dissolved

in dry dichloromethane (10 mL) was added the allenyl-

phosphine (5), (62 mg, 0.138 mmol), and the solution was

heated at reﬂux overnight. The solution was allowed to

cool to room temperature, the solvent removed in vacuo,

and the residue chromatographed on a silica column. Elu-

tion with dichloromethane containing acetone (5%) gave 17

(83.1 mg, 0.097 mmol; 69%) as an orange solid, m.p. 226–

227 °C. Anal. Calc. for C₄₇H₃₆ClN₂O₄PRu ꢂ 0.5CH₂Cl₂:

C, 63.43; H, 4.11; N, 3.08. Found: C, 63.41; H, 4.22; N,

2.77%. A sample suitable for X-ray crystallography was

obtained by diﬀusion of pentane into a dichloromethane

Acknowledgement

We thank Science Foundation Ireland and University

College Dublin for generous ﬁnancial support.

Appendix A. Supplementary material

CCDC 647784, 647787, 647786, 647785, 647791, 647789,

647790, 647788 contain the supplementary crystallographic

data for this paper. These data can be obtained free of charge

from The Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif. Supplementary data

associated with this article can be found, in the online ver-

sion, at doi:10.1016/j.jorganchem.2008.01.046.

1

solution of 17. H NMR (500 MHz, CDCl₃) d 2.98 (1H,

bd, J = 14.5 Hz, H_36a), 4.10 (1H, d, J = 6.0 Hz, H₃₁),

4.45 (1H, dd, J = 6 Hz, 5 Hz, H₃₂), 4.80 (1H, s, H₉), 4.96

(1H, t, J = 5 Hz, H₃₃), 4.98 (1H, bd, J = 14.5 Hz, H_36b),

5.72 (1H, d, J = 5 Hz, H₃₅), 5.76 (1H, d, J = 5 Hz, H₃₄),

6.99 (1H, t, J = 7.5 Hz, H₃), 7.12–7.15 (7H, m, H₂, H₄,

H₁₃, H₁₇, H₁₄, H₁₆, H₁₅), 7.21 (1H, t, J = 7 Hz, H₆),

7.23–7.30 (3H, m, H₅, H₁₉/H₂₃or H₂₀/H₂₂), 7.31 (1H, t,

J = 7 Hz, H₇), 7.37–7.42 (3H, m, H₁₉/H₂₃or H₂₀/H₂₂,

H₂₁), 7.48 (1H, d, J = 7.5 Hz, H₁), 7.53 (1H, d, J = 7 Hz,

H₈), 7.57–7.60 (5H, m, H_25,H₂₉, H₂₆, H₂₈, H₂₇), 7.64

(2H, d, J = 8.3 Hz, H₄₁, H₄₃), 8.02 (2H, d, J = 8.3 Hz,

H₄₀, H₄₄). ¹³C NMR (125 MHz, CDCl₃) d 41.18 (C₃₆),

53.00 (d, J = 10 Hz, C₉), 73.61 (C₃₃), 79.26 (C₃₁), 86.62

(d, J = 12 Hz, C₃₅), 88.60 (C₃₂), 97.31 (C₃₄), 97.87 (d,

J = 53 Hz, C₁₁), 106.93 (C₃₀), 119.43 (C₄), 119.92 (C₅),

123.50 (C₈), 123.90 (C₄₁, C₄₃), 125.21 (C₁), 126.82 (C₇),

126.95 (C₃), 127.07 (C₂), 127.44 (d, J = 6 Hz, C₁₉/₂₃or

C₂₀/C₂₂), 127.90 (C₆), 127.99 (C₁₅), 128.61 (C₄₀, C₄₄),

128.67 (C₁₃/C₁₇or C₁₄/C₁₆), 128.91 (d, J = 11 Hz, C₂₅/

C₂₉or C₂₆/C₂₈), 130.45 (C₂₇), 131.05 (C₂₁), 131.61 (d,

J = 11 Hz, C₂₅/C₂₉or C₂₆/C₂₈), 132.74 (C₁₃/C₁₇or C₁₄/

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Chromium, iron, ruthenium and gold complexes of 3,3-(biphenyl-2,2′-diyl)-1-diphenylphosphino-1-phenylallene: A versatile ligand

DOI: 10.1016/j.jorganchem.2008.01.046

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