Transition metal alkynyl complexes by transmetallation from Au(CΞCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4)

Article abstract of DOI:10.1039/b809960j

Facile acetylide transfer reactions take place between gold(i) complexes Au(CΞCAr)(PPh₃) (Ar = C₆H₅ or C ₆H₄Me-4) and a variety of representative inorganic and organometallic complexes MXL_n

Full text of DOI:10.1039/b809960j

View Article Online / Journal Homepage / Table of Contents for this issue
PAPER
www.rsc.org/dalton | Dalton Transactions
Transition metal alkynyl complexes by transmetallation from
∫
Au(C CAr)(PPh3) (Ar = C6H5 or C6H4Me-4)†
Wan M. Khairul,a,b Mark A. Fox,a Natasha N. Zaitseva,c Maryka Gaudio,c Dmitry S. Yufit,a
Brian W. Skelton,d Allan H. White,d Judith A. K. Howard,a Michael I. Bruce*c and Paul J. Low*a
Received 12th June 2008, Accepted 16th September 2008
First published as an Advance Article on the web 13th November 2008
DOI: 10.1039/b809960j
∫
Facile acetylide transfer reactions take place between gold(I) complexes Au(C CAr)(PPh3) (Ar = C6H5
or C6H4Me-4) and a variety of representative inorganic and organometallic complexes MXLn
(M = metal, X = halide, Ln = supporting ligands) featuring metals from groups 8–11, to afford the
∫
corresponding metal–alkynyl complexes M(C CR)Ln in modest to good yield. Reaction products have
been characterised by spectroscopic methods, and molecular structure determinations are reported for
2
∫
∫
∫
∫
Fe(C CC6H4Me-4)(dppe)Cp, Ru(C CC6H4Me-4)(dppe)Cp*, Ru(C CC6F5)(h -O2)(PPh3)Cp*,
2
∫
∫
Ir(C CC6H4Me-4)(h -O2)(CO)(PPh3)2, Ni(C CC6H4Me-4)(PPh3)Cp and trans-Pt(C CAr)2L2
(Ar = C6H5, L = PPh3; Ar = C6H4Me-4, L = PPh3, PMe3).
carried out at room temperature in ethereal solvents, impli-
Introduction
cate Au(I)–Pd(II) transmetallation processes, and the AuX(PPh3)
by-product can be isolated from the reaction mixture and
recycled.
Transmetallation, defined as the exchange of ligands between
two metal centres,1 is one of the essential reaction steps in
numerous organometallic catalytic cycles, illustrated effectively
by the development of metal-catalysed procedures for the simple
synthesis of C–C, C–N and C–O bonds.2 On a preparative scale,
transmetallation reactions from Sn,3,4 Hg,5,6 Cu7–10 and Ag11
have long been known. However, new aspects of this chemistry
continue to be developed. For example, despite the prevalence of
transmetallation reactions involving alkynyl–copper(I) complexes,
and the growing awareness of gold catalysis in which the transfer
of ligands from gold to other species is involved,12 transmetallation
reactions involving aryl–gold(I) complexes have only recently been
carried out on a variety of transition metal complexes by van
Koten and co-workers.13
Examples of transmetallation involving the readily pre-
18
∫
pared gold(I) species Au(C CR)(PR3) directly in the prepa-
ration of metal alkynyl complexes have been limited to NMR
scale experiments. Shaw and co-workers used 31P NMR spec-
troscopy to follow the acetylide group transfer from Au(I)
to Ni(II) during the facile reaction of NiCl2(dppm-P)2 with
Au(C CC6H5)(PPh3) (CH2Cl2, ca 20 ◦C), which resulted in
∫
∫
the formation of complexes formulated as [Ni(C CC6H5)2(m-
dppm)2Au]Cl (dppm = Ph2PCH2PPh2).19 Cross and Davidson
have used 31P NMR spectroscopy to demonstrate that reac-
∫
tions of cis-PtCl2(PMePh2)2 with Au(C CC6H5)(PPh3) give cis-
∫
and/or trans-Pt(C CC6H5)2(PMePh2)2, depending on the condi-
tions used.20 The same authors reported that reactions of cis-
Transmetallation reactions involving alkynyl–gold(I) com-
plexes are also scarce. Yam and co-workers have prepared
∫
PtCl2(CO)(PMePh2) with Au(C CR)(PPh3) (R = Me, C6H5) gave
1
1
2
the tetranuclear copper(I)–alkynyl complexes [Cu4(m3-h ,h ,h -
∫
cis-Pt(C CR)2(CO)(PMePh2) as the final product via cis- or trans-
∫
C CAr¢)3(PAr3)4]PF6 from the room temperature transmetallation
∫
Pt(C CR)Cl(CO)(PMePh2).
reaction between [Cu(MeCN)4]PF6 and the appropriate alkynyl–
Our long-standing interest in the preparative chemistry of
metal acetylide complexes prompted us to consider the potential
application of alkynyl-gold(I) complexes as reagents for the
preparation of metal acetylides. Gold(I) phosphine complexes
featuring highly conjugated carbon-rich and all-carbon ligands
are known,16,21,22 and are generally easier and safer to handle than
their analogous protio, lithio, tin, copper, mercury or Grignard
derivatives. Convenient transfer of the carbon ligand from gold
to other metals would represent a useful addition to the range of
available synthetic methods for the preparation of metal complexes
containing carbon-rich and all-carbon ligands.16,23
∫
gold(I) polymer [Au(C CAr¢)]• in the presence of phosphines
(PAr3).14 Ferrer and colleagues have observed the ready transfer of
-
∫
4-pyridylethynyl from [Au(C Cpy)2] salts to rhenium following
reaction with [Re(THF)(CO)3(bpy)]OTf.15 The Bruce group has
recently found that cross-coupling reactions of Au(C CR)(PPh3)
with halo-carbynes and halo-acetylenes can be promoted by
Pd(0)/Cu(I) catalyst.16,17 These catalytic reactions, which are
∫
aDepartment of Chemistry, Durham University, South Road, Durham,
UK DH1 3LE
bDepartment of Chemical Sciences, Faculty of Science and Technology,
Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu,
Malaysia
Here, we report transmetallation reactions using the readily
∫
available gold complexes Au(C CAr)(PPh3) [Ar = C6H5 (1a),
cSchool of Chemistry and Physics, University of Adelaide, Adelaide, South
Australia 5005, Australia
C6H4Me-4 (1b)] and representative inorganic and organometallic
compounds MXLn [M = metal, X = halide, Ln = supporting
ligands] featuring metals from groups 8–11 (Scheme 1). The cor-
dChemistry M313, SBBCS, University of Western Australia, Crawley,
Western Australia 6009, Australia
∫
responding metal–alkynyl complexes M(C CAr)Ln are isolated in
† CCDC reference numbers 660622 (4c) and 691297–691304. For crystallo-
graphic data in CIF or other electronic format see DOI: 10.1039/b809960j
their pure form in modest to good yields.
610 | Dalton Trans., 2009, 610–620
This journal is
The Royal Society of Chemistry 2009
©

View Article Online
∫
FeCl(dppe)Cp and Au(C CAr)(PPh3) [Ar = C6H5 (1a), C6H4Me-
4 (1b)] in the presence of NH4PF6 in refluxing MeOH (see
Scheme 2 for a diagrammatic representation of all reactions
reported in this work). Although the solvent and salt combi-
nation was chosen to promote labilisation of the Fe–Cl bond,
the protic conditions also led to formation of the vinylidenes
Scheme 1
= =
[Fe{ C C(H)Ar}(dppe)Cp]PF6. Thus, after reaction, the result-
Results and discussion
ing red solution was treated with DBU and purified by extraction
into benzene and preparative TLC to give the iron–alkynyl
complexes 2a (43%) or 2b (53%). In addition, a colourless band
containing AuCl(PPh3) was also collected (dP 34.2 ppm).29 In the
13C NMR spectra for 2a and 2b, the alkynyl Cb carbons were
identified as broad peaks at 120.7 and 120.3 ppm, respectively.
The alkynyl Ca carbon resonances were very broad (unresolved
Syntheses
∫
Group 8 metal–alkynyl complexes M(C CR)(L2)Cp¢ (M = Fe,
Ru, Os; L = PR3; Cp¢ = Cp, Cp*) have been prepared on
many previous occasions.24–26 The synthesis of such species
usually takes advantage of the ready isomerisation of 1-alkynes
to vinylidenes that takes place in the coordination sphere of
J
CP coupling) peaks at 125.3 and 122.0 for 2a and 2b, respectively,
the group 8 metal centre.27 The resulting cationic vinylidene
with ~150 Hz width at half height. For a series of related
+
=
∫
complexes [M{C C(H)R}(L2)Cp¢] are acidic, and deprotonation
Fe(C CC6H4X-4)(dppe)Cp* (X = NO2, CN, CF, Br, F, H, Me,
occurs readily to give the corresponding acetylide. Whilst the 1-
alkyne–vinylidene–alkynyl conversion has proven to be immensely
useful in the preparation of metal alkynyl complexes of the
tBu, OMe, NH2, NMe2) compounds, the Ca and Cb resonances
were reported as triplets with ca. 40 and 3 Hz coupling constants,
respectively.30
∫
type M(C CR)(L2)Cp¢, it is limited to the use of stable 1-
The reactions between 1a or 1b and RuCl(PPh3)2Cp, in the pres-
ence of NH4PF6 or NaPF6 in refluxing methanol, resulted in the
formation of a red solution, also presumed to contain a vinylidene
intermediate, the deprotonation of which by DBU resulted in the
alkynes. Alternative synthetic routes to metal alkynyl and poly-
ynyl complexes from trimethylsilyl-protected alkynes and poly-
ynes based on desilylation/metallation routes have also been
developed.28
∫
precipitation of the target compounds Ru(C CC6H5)(PPh3)2Cp
The complexes Fe(C CAr)(dppe)Cp [Ar = C6H5 (2a) and
(3a)24 and Ru(C CC6H4Me-4)(PPh3)2Cp (3b)31 as yellow solids in
∫
∫
C6H4Me-4 (2b)] were prepared from the reaction between
81 and 73% yields, respectively. As might be reasonably expected,
Scheme 2
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 610–620 | 611
©

View Article Online
∫
the filtrate recovered from these reactions contained AuCl(PPh3)
of 5a is characterised by n(CO) and n(C C) bands at 2005 and
25
(dP 34.2 ppm).29 The compounds Ru(C CC6H5)(dppe)Cp* (4a)
2134 cm-1, respectively.
∫
31
∫
∫
and Ru(C CC6H4Me-4)(dppe)Cp* (4b) were obtained from
These spectroscopic data from Ir(C CC6H5)(CO)(PPh3)2 ob-
similar reactions of 1a and 1b with RuCl(dppe)Cp*.
The alkynyl–gold transmetallation reaction appears to be
sensitive to the nature of the alkynyl moiety, and a reaction
served in situ and authentic samples of 5a can be compared
∫
with those reported for Ir(C CC6H5)(CO)(PPh3)2 (dP < 10 ppm,
n(CO) ca. 1960 cm-1) by two independent research groups,38,39 and
∫
∫
between RuCl(PPh3)2Cp* and Au(C CC6F5)(PPh3) (1c) afforded
Ir{C CC(CH2CH2Ph)2Me}(CO)(PPh3)2 (dP ca. 22 ppm, n(CO)
a multitude of products as indicated by separation into several
bands upon preparative TLC. One of these bands gave crystals
from hexane suitable for a single-crystal X-ray diffraction study
(see below) from which the compound was identified as the
1970 cm-1).40 It appears that the 31P NMR spectra reported
2
∫
previously for Ir(C CC6H5)(CO)(PPh3)2 are actually that of the h -
O2 containing species 5a, although the IR data in the earlier reports
are consistent with the proposed 16 e species. It can be concluded
31
∫
∫
dioxygen complex Ru(C CC6F5)(h-O2)(PPh3)Cp* (4c). The anal-
that the characteristic P resonances for Ir(C CR)(CO)(PPh3)2
2
∫
∫
ogous hydrocarbon complex Ru(C CC6H5)(h-O2)(PPh3)Cp* is
and Ir(C CR)(h -O2)(CO)(PPh3)2 compounds are found at ca.
known.32
25 ppm and ca. 5 ppm, respectively. These parameters are
Although complete mechanistic details of the transmetallation
reaction have not been elucidated, it is important to note that 1a or
1b can be recovered unchanged after treatment for 1 h in refluxing
methanol containing one equivalent of NH4PF6. This observation
would appear to discount the possible solvolysis of 1a or 1b to give
the free alkyne, followed by the usual vinylidene formation, and
supports the intermediacy of the gold reagents in the formation of
the new metal–carbon bonds.
consistent with those found for other Ir(R)(CO)(PPh3)2 and
2
Ir(R)(h -O2)(CO)(PPh3)2 systems.41
Group 10 alkynyl complexes have been prepared on numerous
occasions, being among the earliest metal–alkynyl complexes
characterised.42 Whilst early synthetic routes took advantage of
nucleophilic reactions between alkynyl anions (as lithium salts
or Grignard reagents), later developments have given rise to
more convenient preparations involving CuI-catalysed reactions
between, for example, MCl2(PR3)2 and 1-alkynes.8
In the case of group 9 metals, alkynyl complexes such
∫
as Ir(C CR)(CO)(PPh3)2 have been prepared by reactions of
The reaction of 1a or 1b with NiBr(PPh3)Cp in THF
Vaska’s complex, IrCl(CO)(PPh3)2, or its NCMe derivative,
with lithium acetylides or trialkylstannyl acetylenes,3,33 and
also from copper-catalysed reactions between IrCl(CO)(PPh3)2
and 1-alkynes carried out in amine solvents or in the pres-
resulted in the formation of
a
green solution, from
which Ni(C CC6H5)(PPh3)Cp (6a)42 or the new complex
∫
∫
Ni(C CC6H4Me-4)(PPh3)Cp (6b) were obtained in 53 and 42%
yields, respectively, after preparative TLC and recrystallisation. In
addition, a colourless band from preparative TLC that contained
the expected by-product AuBr(PPh3) was also collected (dP
36.3 ppm).29
ence of NaOMe.8 The complexes Ir(C CR)(CO)(PR¢3)2 read-
∫
2
2
∫
ily take up oxygen to form the h -O2 adducts Ir(C CR)(h -
O2)(CO)(PR¢3). For example, the CuI-catalysed reaction be-
tween W(C CC CH)(CO)3Cp and Vaska’s complex in NHEt2
∫
∫
∫
The complexes trans-Pt(C CAr)2(PPh3)2 [Ar = C6H5 (7a),
gave {Cp(CO)3W}(m-C CC C){Ir(CO)(PPh3)2}, which on aero-
C6H4Me-4 (7b)8] were prepared from room temperature reactions
between cis-PtCl2(PPh3)2 and 1a or 1b in methanol, which gave the
products as pale cream coloured precipitates, whilst AuCl(PPh3)
was recovered from the filtrate.‡ The 31P NMR spectra contain
singlet phosphine resonances, each accompanied by platinum
satellites, confirming the trans geometry in each case. The com-
∫
∫
2
bic work-up gave the h -O2 adduct.34
2
∫
In the present work, the complexes Ir(C CAr)(h -O2)(CO)-
(PPh3)2 [Ar = C6H5 (5a),33,35 C6H4Me-4 (5b)] were prepared
by treating IrCl(CO)(PPh3)2 with 1a or 1b in MeOH at room
temperature. The gold by-product AuCl(PPh3) was removed from
the crude product by extraction with acetone. Recrystallisation
(chloroform/hexane) of the yellow solid that remained after
extraction under aerobic conditions afforded yellow crystals of
5a (40%) or 5b (52%). In order to resolve some inconsisten-
cies in literature values relating to the 31P NMR spectra and
∫
plexes trans-Pt(C CAr)2(PMe3)2 [Ar = C6H5 (8a), C6H4Me-4 (8b)]
were isolated from similar reactions between cis-PtCl2(PMe3)2 and
1a or 1b in methanol, which gave the products as pale green
precipitates. Single crystals of 8b suitable for X-ray diffraction
were obtained by recrystallisation (CHCl3/MeOH).
hence potentially the n(CO) band positions associated with
The room temperature reaction of 1a with a large excess of cis-
PtCl2(PMe3)2 in the presence of NH4PF6 in methanol resulted
in a myriad of products. The solids obtained after removal
36,37
∫
16 e acetylide complexes Ir(C CAr)(CO)(PPh3)2,
and also
to clarify the sequence of reactions leading to the dioxygen
2
∫
∫
adducts Ir(C CAr)(h -O2)(CO)(PPh3)2 obtained here, the trans-
of the solvent included trans-PtCl(C CC6H5)(PMe3)2 and trans-
metallation/oxidation reaction sequence was followed by 31P
NMR and IR spectroscopy. Under anaerobic conditions, reaction
solutions of 1a and Vaska’s complex rapidly developed new 31P
resonances at 34.2 and 25.2 ppm corresponding to AuCl(PPh3)29
PtCl(C CC6H5)(PMe3)(PPh3), which were identified by NMR
∫
spectrocopy and MS spectrometry. Crystallisation of the solids
from MeCN/MeOH gave crystals of a Au(I) salt [Au(PMe3)2]PF6
(9).43 Thus, it appears that phosphine exchange, competitive with
the acetylide–halide exchange processes noted above, may also
take place under certain conditions.
∫
and Ir(C CC6H5)(CO)(PPh3)2, respectively. The n(CO) band of
the acetylide complex (1962 cm-1) is almost coincident with
∫
that of Vaska’s complex, although the n(C C) band is distinct
Given the established utility of copper acetylides in the prepa-
ration of many transition metal acetylide complexes, we were
(2128 cm-1). Exposure of the reaction solution to air resulted
in the rapid disappearance of the dP 25.2 ppm peak and the
2
∫
appearance of a peak at 8.3 ppm corresponding to Ir(C CPh)(h -
‡ In the process of crystallization of the complex 7b, crystals of previously
unknown chloroform di-solvate of trans-PtCl2(PPh3)2 were isolated and
structurally studied.†
O2)(CO)(PPh3)2 5a, consistent with spectroscopic analysis of the
crystallographically characterised sample of 5b. The IR spectrum
612 | Dalton Trans., 2009, 610–620
This journal is
The Royal Society of Chemistry 2009
©

View Article Online
Table 1 Crystallographic and refinement details†
Complex
Formula
2b
4b
4c
5b
6b
7a
7b
8b
C40H36FeP2·
CH2Cl2
676.94
C45H46P2Ru
C36H30F5O2PRu· C46H37IrO3P2· C32H27NiP
C52H40P2Pt
921.9
Orthorhombic Monoclinic
Pbca
120(2)
17.9771(3)
9.5527(1)
22.9326(3)
90
90
90
3938.2(1)
4
1.555
3.7
C54H44P2Pt
949.9
C24H32P2Pt
0.25C6H14
743.2
CHCl3
1011.3
Monoclinic
P21/c
120(2)
9.7735(3)
19.5550(4)
22.3273(6)
90
99.18(2)
90
4212.6(2)
4
MW
749.83
Monoclinic
P21/c
501.22
Monoclinic
P21/n
120(2)
14.1937
12.6191(4)
14.9549(4)
90
110.05(1)
90
2516.19(13)
4
577.5
Monoclinic
P21/c
Crystal system
Space group
T/K
Triclinic
Triclinic
¯
¯
P1
P1
P21/n
120(2)
13.5550(2)
8.5121(1)
18.0271(3)
90
90.30(1)
90
2079.97(5)
2
120(2)
120(2)
100(2)
120(2)
12.3805(5)
5.7372(2)
17.1229(7)
90
105.86(1)
90
1169.92(8)
2
˚
a/A
9.5283(2)
18.2097(4)
19.3123(4)
93.20(2)
93.13(2)
97.83(2)
3307.85(12)
4
15.4106(3)
11.2059(2)
22.1850(4)
90
108.33(1)
90
3636.75(12)
4
1.369
13.027(4)
16.959(5)
17.133(6)
111.86(3)
106.93(3)
93.67(2)
3297(2)
4
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
3
˚
V/A
Z
rc/g cm-3
1.359
1.497
0.59
27 359
1.595
3.5
37 675
1.323
0.853
34 844
1.517
3.5
25 528
1.639
6.1
10 382
m(MoKa)/mm-1 0.662
0.551
48 050
Nt
N (Rint
71 399
51 715
)
18 098 (0.041) 10 598 (0.045) 11 685 (0.089)
9167 (0.116) 7062 (0.029) 5741 (0.045)
5541 (0.035) 3307 (0.025)
R1 [I > 2s(I)]
wR2 (all data)
GOF
0.040
0.097
1.088
0.033
0.093
1.063
0.063
0.076
0.953
0.070
0.120
1.087
0.029
0.079
1.017
0.018
0.051
1.053
0.017
0.041
1.095
0.018
0.041
1.098
interested in the interplay between acetylide ligands and Cu(I)
and Au(I) centres. The reaction between 1a or 1b and CuI in THF
afforded striking, bright yellow-coloured precipitates of the copper
∫
acetylides {Cu(C CAr)}n [Ar = C6H5 (10a), C6H4Me-4 (10b)] in
very good yields with AuI(PPh3) recovered from the filtrate as a
cream-coloured solid (dP 40.0 ppm).29
Molecular structures
The molecular structures of a number of the compounds prepared
in this work (2b, 4b, 4c, 5b, 6b, 7a, 7b and 8b) have been determined
by single-crystal X-ray diffraction studies. The crystallographic
data are summarised in Table 1.
∫
Crystals of Fe(C CC6H4Me-4)(dppe)Cp (2b), obtained from
CH2Cl2/hexane solutions, contain two independent molecules,
which differ by the relative orientation of the phenyl rings on
the dppe ligand, together with a molecule of CH2Cl2. There are
no differences of chemical significance in the two independent
molecules, and the geometrical parameters of only one molecule
will be used in further discussion here. Although there are
many examples of crystallographically characterized arylacetylide
complexes of the Fe(dppe)Cp* fragment in both formal Fe(II)
and Fe(III) oxidation states,30,44–48 polymetallic compounds45,49 and
mixed valence examples,44,50 there are surprisingly few struc-
tures of similar compounds containing the Fe(dppe)Cp51,52 or
Fe(dppm)Cp53 fragments reported to date.
∫
Fig. 1 A plot of one molecule of Fe(C CC6H4Me-4)(dppe)Cp (2b), show-
ing the atom labelling scheme. Hydrogen atoms in this and other figures are
◦
˚
removed for clarity. Selected bond lengths (A) and angles ( ): Fe(1)–C(1)
1.907(2); Fe(1)–P(1) 2.1687(6); Fe(1)–P(2) 2.1714(7); C(1)–C(2) 1.220(2);
C(2)–C(3) 1.439(2); P(1)–Fe(1)–P(2) 85.95(2); C(1)–Fe(1)–P(1) 90.19(5);
C(1)–Fe(1)–P(2) 84.28(5); Fe(1)–C(1)–C(2) 174.93(15); C(1)–C(2)–C(3)
174.84(17).
∫
Fe(C CC6H4-Me)(dppe)Cp* might be taken as an indication of
steric interactions between the bulky Cp* and dppe ligands. The
Fe(1)–C(1)–C(2)–C(3) fragment in 2b is essentially linear, with
small deviations likely to be due to packing effects rather than any
profound electronic phenomenon. The plane containing the C(3)–
C(8) aromatic ring forms a dihedral angle of 38.6(1)◦ with the
plane of the Cp ring; the significance of the aryl group orientation
on the electronic structure of iron aryl acetylide complexes has
been discussed elsewhere.48
Complex 2b (Fig. 1) offers a pseudo-octahedral environment
at the metal centre, typical of three-legged piano-stool com-
˚
˚
∫
plexes. The Fe(1)–C(1) [1.907(2) A], C(1) C(2) [1.220(2) A] and
˚
C(2)–C(3) [1.439(2) A] bond lengths in 2b are indistinguishable
∫
from those found in Fe(C CC6H4-Me)(dppe)Cp* [Fe–Ca 1.896(3),
47
˚
∫
Ca Cb 1.220(4), Cb-Cipso 1.440(4) A], but somewhat surprisingly
˚
the Fe–P bonds in 2b [2.1687(6) and 2.1714(7) A], and related
compounds,51 are shorter than in the Cp* analogue [2.1829(8)
The disposition of the tolyl ring with respect to the metal
fragment in the ruthenium complex 4b (Fig. 2) is similar to
that found in 2b. The Ru(1)–C(1) bond length [2.0205(19) A] is
˚
and 2.1924(7) A]. Since the more electron-rich, Cp*-substituted
˚
metal fragment might be expected to induce more effective
Fe–P back-bonding, the relatively elongated Fe–P bonds in
somewhat longer than in 2b, reflecting the difference inthe covalent
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 610–620 | 613
©

View Article Online
and elsewhere. The dioxygen molecule is unsymmetrically attached
˚
to Ru [Ru–O(1;2) 2.042(4), 2.039(4); 1.998(4), 2.019(4) A], prob-
ably as a result of differing trans influences of the P and C(1)
˚
atoms. The O(1)–O(2) separations are 1.404(4) and 1.400(4) A.
These values are similar to those found in the related non-
2
∫
fluorinated complex Ru(C CC6H5)(h -O2)(PPh3)Cp*, which has
Ru–P 2.327(1), Ru–C(cp) 2.25 (av.), Ru–C(1) 2.022(4), C(1)–C(2)
1.158(5), C(2)–C(21) 1.467(5) and Ru–O 2.032(3), 2.048(3), O–
32
˚
O 1.364(4) A. In both complexes, the Ru–O distances are
longer, and the O–O distances shorter, than those found in
2
related cations, such as [Ru(h -O2)(dppm)Cp*]+, which has Ru–
56
˚
O 2.003(9), 2.002(9), O–O 1.37(1) A.
Although dioxygen adducts of Vaska’s complex and derivatives
are well known, crystallographically characterised examples are
surprisingly rare,41,57,58 and to the best of our knowledge, the diyn-
2
∫
∫
diyl complex {(PPh3)(CO)(h -O2)Ir}(m-C CC C){W(CO)3Cp} is
the only example of a dioxygen adduct of a Vaska-type acetylide
derivative that has been structurally characterised to date.34 How-
ever, given the relatively low precision of the diyndiyl structure,
∫
Fig. 2 A plot of one molecule of Ru(C CC6H4Me-4)(dppe)Cp* (4b),
˚
showing the atom labelling scheme. Selected bond lengths (A) and angles
2
59
5b is most conveniently compared with IrCl(h -O2)(CO)(PPh3)2
and Ir(C CC6H5)(CO)(PPh3)2.
(◦): Ru(1)–C(1) 2.0205(19); Ru(1)–P(1) 2.2621(5); Ru(1)–P(2) 2.2622(5);
C(1)–C(2) 1.211(3); C(2)–C(3) 1.437(3); P(1)–Ru(1)–P(2) 83.15(2);
C(1)–Ru(1)–P(1) 79.22(5); C(1)–Ru(1)–P(2) 85.20(6); Ru(1)–C(1)–C(2)
175.5(2); C(1)–C(2)–C(3) 171.9(2).
39
∫
The structure of the complex 5b (Fig. 4) can be described in
terms of a five-coordinate, trigonal bipyramid, if the O2 ligand
is assumed to occupy a single coordination site, with C(1), C(4)
and the midpoint of the O2 ligand defining the equatorial plane
[C(1)–Ir(1)–C(4) 94.5(4), C(1)–Ir(1)–O(0) 137, C(4)–Ir(1)–O(0)
128◦ (O(0) is the midpoint of the O–O bond)]. Alternatively, the
structure may be viewed as a highly distorted octahedron58–60 in
keeping with a formal description of the complex in terms of
radii of the two metals,54 but within the range noted for similar
compounds, including 4a, noted here and elsewhere.55 Other metric
parameters are unremarkable (Fig. 2).
The molecular structure of Ru(C CC6F5)(h -O2)(PPh3)Cp*
(4c) (Fig. 3) is formally related to that of Ru(C CC6H5)(h-
2
∫
∫
˚
O2)(PPh3)Cp* by replacement of the C6H5 group on the acetylide
ligand by C6F5. Two molecules of the complex 4c, devoid of
crystallographic symmetry, together with one half of a centrosym-
metric hexane solvent molecule, comprise the asymmetric unit of
the structure. The two independent molecules differ slightly by
orientations of one of the phenyl rings and C6F5 group. Structural
parameters are similar to those found for many other examples
of half-sandwich ruthenium alkynyl complexes characterised here
an Ir(III)-peroxo complex. The O–O bond is long [1.492(9) A]
˚
and the Ir–P bonds [Ir(1)–P(1,2) 2.351(2) and 2.350(2) A] are
slightly elongated in comparison with those in the well defined Ir(I)
˚
∫
acetylide complex Ir(C CC6H5)(CO)(PPh3)2 [2.286(7)–2.313(9) A
2
∫
Fig. 4 Molecular structure of Ir(C CC6H4Me)(h -O2)(CO)(PPh3)2 (5b).
◦
2
˚
∫
Fig. 3 A projection of one molecule of Ru(C CC6F5)(h -O2)(PPh3)Cp
Selected bond lengths (A) and angles ( ): Ir–P(1) 2.351(2); Ir–P(2) 2.350(2);
(4c). Selected bond lengths (A) and angles (◦) for two indepen-
Ir–C(1) 1.844(10); Ir–C(4) 2.011(10); C(4)–C(5) 1.186(12); C(5)–C(6A)
1.466(16); C(5)–C(6B) 1.484(18); Ir–O(2) 2.030(7); Ir–O(3) 2.036(7);
O(2)–O(3) 1.492(9); P(1)–Ir–P(2) 175.58(8); C(1)–Ir–C(4) 94.5(4);
C(4)–Ir–O(2) 106.9(3); C(4)–Ir–O(3) 149.8(3); C(1)–Ir–O(3) 115.7(4);
Ir–C(4)–C(5) 177.4(7); C(4)–C(5)–C(6A)172.5(12); C(4)–C(5)–C(6B)
178.3(12).
˚
dent molecules: Ru–P(1) 2.328(2), 2.313(2); Ru–C(Cp) 2.214–2.273(6),
2.202–2.289(6) [<av.> 2.24(3), 2.25(4)]; Ru–C(1) 1.997(6), 2.006(7);
C(1)–C(2) 1.187(7), 1.198(7); C(2)–C(3) 1.429(8), 1.455(8); P(1)–Ru–C(1)
85.0(2), 82.2(2); Ru–C(1)–C(2) 178.7(6), 178.8(6); C(1)–C(2)–C(3)
176.0(7), 177.6(7).
614 | Dalton Trans., 2009, 610–620
This journal is
The Royal Society of Chemistry 2009
©

View Article Online
2
over two independent molecules], and similar to those in IrCl(h -
˚
O2)(CO)(PPh3)2 [2.38(1), 2.36(1) A]. Thus, whilst formalised
descriptions of metal oxidation states in organometallic chemistry
are not always especially useful, it seems appropriate to consider 5b
and compounds of this type as Ir(III), with a significant distortion
from the trigonal bipyramidal geometry towards an octahedral
structure.
∫
The molecular structures of nickel(II) complexes Ni(C CR)-
(PPh3)Cp have been studied on previous occasions, with data
often interrogated for evidence of the nature of the metal–
acetylide bond.61,62 The structure of 6a has been reported by the
Humphrey group,61 and unsurprisingly, the structure of 6b (Fig. 5)
˚
is similar. The Ni(1)–C(1) bond lengths in 6a [1.856(3), 1.850(3) A]
˚
and 6b [1.8537(14) A] are indistinguishable, and whilst there is
greater variation in the lengths of the Ni(1)–P(1) [6a 2.1350(9),
˚
∫
2.1378(9); 6b 2.1456(3) A] and C(1) C(2) [6a 1.191(4), 1.193(4);
Fig. 6 A projection of the molecular structure of centrosymmetric
˚
˚
∫
6b 1.2150(19) A] bonds, the parameters associated with 6b fall
trans-Pt(C CC6H5)2(PPh3)2 (7a). Selected bond lengths (A) and angles
(◦): Pt–P(1) 2.3121(4); Pt–C(1) 2.0017(17); C(1)–C(2) 1.207(2); C(2)–C(3)
1.441(2); P(1)–Pt–C(1) 93.27(5); Pt–C(1)–C(2) 172.78(15); C(1)–C(2)–C(3)
173.27(18). [symmetry operations (-x, 1 - y, -z)].
within the ranges defined by many other similar compounds. The
Ni(1)–C(1)–C(2)–C(3) moiety is essentially linear with angles at
C(1) and C(2) being 175.1(1) and 172.2(1)◦, respectively.
∫
Fig. 5 A plot of a molecule of Ni(C CC6H4Me-4)(PPh3)Cp (6b).
◦
˚
Selected bond lengths (A) and angles ( ): Ni(1)–P(1) 2.1456(3); Ni(1)–C(1)
1.8537(14); C(1)–C(2) 1.2150(19); C(2)–C(3) 1.4416(18); C(1)–Ni(1)–P(1)
89.10(4); Ni(1)–C(1)–C(2) 175.1(1); C(1)–C(2)–C(3) 172.2(1).
Fig.
7
The molecular structure of centrosymmetric trans-
◦
˚
∫
Pt(C CC6H4Me)2(PPh3)2 (7b). Selected bond lengths (A) and angles ( ):
Pt–P(1) 2.2887(4); Pt–C(1) 2.0252(17); C(1)–C(2) 1.188(2); C(2)–C(3)
1.445(2); P(1)–Pt–C(1) 85.90(5); Pt–C(1)–C(2) 175.88(15); C(1)–C(2)–C(3)
177.32(18). [symmetry operations (1 - x, -y, -z)].
In each of the Pt(II) complexes 7a (Fig. 6) and 7b (Fig. 7), the
metal atoms of the molecules are located in special positions at
the crystallographic inversion centre, the platinum centres being
in square-planar arrangements, with bond lengths comparable to
those in many other similar platinum bis(acetylide) complexes.63
The ethynyl moieties are essentially linear [Pt(1)–C(1)–C(2)
172.78(15) (7a)◦; 175.9(2) (7b)◦, C(1)–C(2)–C(3) 173.27(18) (7a);
∫
177.32(18) (7b) ] and the acetylenic (C C) and Pt(1)–C(1) bond
lengths fall in a narrow range [1.188(2)–1.207(2) and 2.0017(17)–
˚
2.0252(17) A, respectively] typical for these systems.
While there are examples of platinum bis(acetylide) complexes
known, there is only one previous example of the structurally
characterised trans-Pt(C CR)2(PMe3)2 system.64 A comparison
∫
Fig.
8
A
plot of
a
molecule of centrosymmetric trans-
of the structural parameters of 8b (Fig. 8) and the Pt moiety
in the cyclic heteronuclear complex [{Au{Pt(PMe3)2}2}{1,2-m-
˚
∫
Pt(C CC6H4Me)2(PMe3)2 (8b). Selected bond lengths (A) and angles
(◦): Pt–P(1) 2.2929(6); Pt–C(1) 2.0001(3); C(1)–C(2) 1.214(4); C(2)–C(3)
1.437(3); P(1)–Pt–C(1) 89.55(7); Pt–C(1)–C(2) 178.7(2); C(1)–C(2)–C(3)
175.3(3). [symmetry operations (1 - x, 2 - y, -z)].
∫
C6H4(C C)2}3] reveals little differences and indicates that the
constraining effect at the Pt atom in the cyclic complex is negligible.
The change of the phosphine ligand in 7b and 8b has little effect
on the overall molecular structure.
with additional CH(Me) ◊ ◊ ◊ C(sp) close intermolecular contacts
(C ◊ ◊ ◊ H 2.83 A). In molecule 7a, no methyl groups are present
while in the structure 8b, trimethylphosphine groups take part in
intermolecular CH ◊ ◊ ◊ p contacts and impede parallel arrangement
of tolyl groups. It seems that in the case of these Pt complexes,
˚
Considering the intermolecular interactions in these three
platinum complexes, stacking-type p ◊ ◊ ◊ p interactions between
tolyl groups were observed only in the structure 7b (Fig. 9)
˚
(interplanar distance is equal to 3.64 A) where they are combined
This journal is The Royal Society of Chemistry 2009
Dalton Trans., 2009, 610–620 | 615
©

View Article Online
with silica gel (0.5 mm thick, Merck GF-254). The reagents
FeCl(dppe)Cp,66 RuCl(PPh3)2Cp,67 RuCl(PPh3)2Cp*,32 RuCl-
(dppe)Cp*,68 NiBr(PPh3)Cp,69 cis-PtCl2(PPh3)2,70 cis-PtCl2-
18
(PMe3)2,71 IrCl(CO)(PPh3),72 Au(C CC6H5)(PPh3) (1a), Au(C
∫
∫
CC6H4Me-4)(PPh3) (1b)18 and Au(C CC6F5)(PPh3) (1c) were
prepared by literature methods. Other reagents were purchased
and used as received.
18
∫
IR spectra were recorded from dichloromethane solutions in
a cell fitted with CaF2 windows, from KBr discs, or from Nujol
mulls between NaCl plates using a Nicolet Avatar spectrometer.
NMR spectra were obtained with Bruker Avance and Varian
Mercury spectrometers from CDCl3 solutions and referenced
against solvent resonances (1H, 13C) or external H3PO4 (31P). The
31P chemical shift values for the gold starting materials 1a and 1b
are at 43.4 ppm. Mass spectra were recorded using Thermo Quest
Finnigan Trace MS-Trace GC or Thermo Electron Finnigan LTQ
FT mass spectrometers.
Fig. 9 A fragment of the crystal structure of (7b) showing the stacking
interactions between tolyl groups.
stacking interactions alone are insufficient to determine the
packing of molecules in the crystal.
The series of acetylide complexes reported here all feature small
∫
deviations from linearity along the M–C C–CAr chain, which are
consequently gently curved or bowed. In a comprehensive review
of polyyne conformation and structure, Szafert and Gladysz have
noted a lack of systematic variation in structure within the solid
state within a large array of yne-based compounds.65 Given the
∫
∫
low bending force constants associated with M–C C and C C–C,
crystal packing effects are thought likely to be responsible for the
specific conformation adopted by any one compound.
∫
Preparation of Fe(C CC6H5)(dppe)Cp (2a)
A suspension of FeCl(dppe)Cp (50 mg, 0.09 mmol), 1a (51 mg,
0.09 mmol) and NH4PF6 (15 mg, 0.09 mmol) in MeOH (10 ml)
was heated at reflux for ca. 1 h, the progress of the reaction
being monitored by TLC (hexane–acetone = 7 : 3). The resulting
clear orange solution was treated with 2–3 drops of DBU and
the reaction mixture was taken to dryness. The crude solid was
extracted with benzene, and the extracts purified by preparative
TLC (hexane–acetone = 7 : 3). The red band was collected and
Finally, we note that while our work was in progress, the
structure of 9 was independently reported by Horvarth and
Raubenheimer.43 The conclusions drawn by these authors are
consistent with our own observations from an essentially identical
structure determination, and no further comment is necessary.
Conclusions
-1
1
∫
afforded 2a (24 mg, 43%). IR (CH2Cl2) n/cm : (C C) 2060. H
NMR d/ppm: 2.23 (m, 2H, dppe), 2.63 (m, 2H, dppe); 4.25 (s, 5H,
Cp), 6.49 (2H, d, phenyl C2H of C CC6H5), 6.81 (1H, t, C4H),
A series of preparative scale, stoichiometric transmetallation
reactions involving alkynyl–gold(I) complexes, Au(C CR)(PPh3)
∫
∫
6.92 (2H, dd, C3H), 7.26 (m, 10H, dppe), 7.41 (m, 6H, dppe), 7.94
(R = Ph, C6H4Me-4), and inorganic or organometallic compounds
1
1
(m, 4H, dppe). 31P{ H} NMR d/ppm: 107.5 (s, dppe). 13C{ H}
NMR d/ppm: 28.6 (m, dppe CH2); 79.3 (Cp); 120.7 (Cb); 123.1
(C4), 125.3 (br, Ca), 127.5 (C3); 127.8, 128.1 (dd, 3JCP,5JCCP~5 Hz,
MXLn (M = metal, X = halide, Ln = supporting ligands), have
∫
afforded the corresponding metal alkynyl complexes M(C CR)Ln,
(35–90% yields), with representative examples featuring metals
from groups 8–11 being described for the first time. The alkynyl
products were fully characterised by the usual spectroscopic meth-
ods and molecular structural analyses in several cases. Looking
ahead, we note that easily prepared phosphine–gold(I) complexes
featuring highly conjugated carbon-rich and all-carbon ligands
are known, and which are usually easier and safer to handle than
their analogous protio, lithio, tin, copper, mercury or Grignard
derivatives. The AuX(PPh3) by-products can be isolated from the
reaction mixture and recycled. The transmetallation process has
not been as successful with Au(C CC6F5)(PPh3) based on one
exploratory reaction here. Further investigations are desirable with
other Au(C CAr)(PR3) complexes to assess the generality of the
alkynyl–gold transmetallation process and also to understand the
alkynyl–gold transmetallation mechanism.
C
m,m¢); 129.0, 129.4 (Cp,p¢); 130.1 (C1); 130.5 (C2); 132.0, 134.0 (dd,
2JCP,4JCCP~5, Co,o¢); 138.2, 142.5 (m, Ci,i¢). Found: C 75.2, H 5.6%.
C39H34P2Fe requires: C 75.5, H 5.5%. ES-MS: m/z 621 [M + H]+,
+
∫
519 [M - C CPh] . High resolution calculated for FeC39H34P2:
[M]+: 620.14797; found: 620.14757.
∫
Preparation of Fe(C CC6H4Me-4)(dppe)Cp (2b)
Complex 2b (62 mg, 54%) was formed from FeCl(dppe)Cp
(100 mg, 0.18 mmol), 1b (103 mg, 0.18 mmol) and NH4PF6
(30 mg, 0.18 mmol) in MeOH (20 mL) using a similar procedure as
described for 2a. Crystals of 2b suitable for X-ray crystallography
were grown from slow diffusion of hexane into a CH2Cl2 solution.
∫
∫
-1
1
∫
IR (CH2Cl2) n/cm : (C C) 2067. H NMR d/ppm: 2.16 (s, 3H,
CH3), 2.21 (m, 2H, dppe), 2.60 (m, 2H, dppe), 4.23 (s, 5H, Cp),
6.38 (2H, d, tolyl C2H), 6.72 (2H, dd, C3H), 7.26 (m, 10H, dppe),
Experimental
7.40 (m, 6H, dppe), 7.93 (m, 4H, dppe). 31P{ H} NMR d/ppm:
1
1
All reactions were carried out under an atmosphere of nitro-
gen using standard Schlenk techniques. Reaction solvents were
purified and dried using an Innovative Technology SPS-400
system, and degassed before use. No special precautions were
taken to exclude air or moisture during work-up. Preparative
TLC was performed on 20 ¥ 20 cm glass plates coated
107.3 (s, dppe). 13C{ H} NMR d/ppm: 21.0 (s, CH3), 28.3 (m,
dppe CH2), 78.9 (Cp), 120.3 (Cb), 122.0 (br, Ca), 126.9 (C1), 127.5,
127.8 (dd, 3JCP,5JCCP~5 Hz, Cm,m¢), 128.0 (C3), 128.6, 129.0 (Cp,p¢),
130.0 (C2), 132.3 (C4), 131.7, 133.7 (dd, 2JCP,4JCCP~5, Co,o¢), 138.1,
142.3 (m, Ci,i¢). Found: C 75.6, H 5.7%. C40H36P2Fe requires: C
75.7, H 5.7%. ES-MS(+): m/z 635 [M + H]+.
616 | Dalton Trans., 2009, 610–620
This journal is
The Royal Society of Chemistry 2009
©

View Article Online
∫
Preparation of Ru(C CC6H5)(PPh3)2Cp (3a)
C6H4), 6.81 (d, 2H, JHH = 8 Hz, C6H4), 7.39 (m, 12H, PPh3), 7.45
1
(m, 6H, PPh3), 7.59 (m, 12H, PPh3). 31P{ H} NMR d/ppm: 8.3
A suspension of RuCl(PPh3)2Cp (100 mg, 0.14 mmol), 1a (77 mg,
0.14 mmol) and NH4PF6 (22 mg, 0.14 mmol) in MeOH (10 mL)
was heated at reflux point for 30 min to form a bright red solution.
Addition of 2–3 drops of DBU caused a yellow precipitate to
form, which was collected by filtration, washed with cold MeOH
(3 mL), and air-dried to afford 3a as a yellow solid (88 mg, 81%)
and characterised by comparison of spectroscopic data with those
reported elsewhere.24,31
1
(s). 13C{ H} NMR d/ppm: 67.8 (t, 2JCP 11 Hz, Ca), 108.5 (s, Cb),
125.1 (C4), 127.3 (C3), 128.1 (dd, 3JCP, 5JCP~5 Hz, Cm), 128.1 (m,
Ci), 128.2 (C1), 130.8 (Cp), 131.3 (C2), 134.7 (dd, 2JCP, 4JCP~5 Hz,
+
∫
Co), 167.1 (s, C O). ES-MS: m/z 879 [M + H] , 920 [M + H +
MeCN]+.
2
∫
Preparation of Ir(C CC6H4Me-4)(g -O2)(CO)(PPh3)2 (5b)
A suspension of IrCl(CO)(PPh3)2 (100 mg, 0.13 mmol) and 1b
(74 mg, 0.13 mmol) were stirred at room temperature in THF
(12 mL) for ca. 6 h to give an orange solution. After the same work-
up as described above for 5a, the yellow solid was recrystallised
∫
Preparation of Ru(C CC6H4Me-4)(PPh3)2Cp (3b)
Complex 3b (84 mg, 74%) was formed from 1b and
RuCl(PPh3)2Cp, using a similar procedure to that described for
3a, and identified by comparison with an authentic sample.31
from CHCl3/hexane to yield yellow crystals of 5b (46 mg, 40%)
-1
∫
suitable for X-ray crystallography. IR (CH2Cl2) n/cm : (C C)
1
∫
2128; (C O) 2008, (O–O) 834. H NMR d/ppm: 2.23 (s, 3H, Me),
∫
Preparation of Ru(C CC6H5)(dppe)Cp* (4a)
6.24 (d, 2H, JHH = 8 Hz, C6H4), 6.81 (d, 2H, JHH = 8 Hz, C6H4),
7.39 (m, 12H, PPh3), 7.45 (m, 6H, PPh3), 7.59 (m, 12H, PPh3).
A suspension of RuCl(dppe)Cp* (100 mg, 0.15 mmol), 1a (84 mg,
0.15 mmol) and NH4PF6 (24 mg, 0.15 mmol) in MeOH (10 mL)
was heated at reflux point for 1 h to form a bright red solution,
which was treated with 2–3 drops of DBU and allowed to stir for a
further 1 h. The yellow precipitate that formed over this time was
collected by filtration, washed with cold MeOH (3 mL), and air-
dried to afford 4a as a yellow solid (56 mg, 51%). Characterisation
data for 4a were identical to that reported elsewhere.31,55
1
1
31P{ H} NMR d/ppm: 8.2 (s). 13C{ H} NMR d/ppm: 21.1 (s,
2
Me), 66.0 (t, JCP 11 Hz, Ca), 109.1 (s, Cb), 125.0 (C1), 128.1
(C3), 131.1 (C2), 134.8 (C4), 128.1 (dd, JCP, JCP~5 Hz, Cm),
3
5
2
4
128.1 (m, Ci), 130.7 (Cp), 134.6 (dd, JCP, JCP~5 Hz, Co), 167.1
∫
(s, C O). Found: C 61.5, H 4.1%. C46H37P2O3Ir requires: C 62.0,
H 4.2%. ES-MS: m/z 893 [M + H]+, 934 [M + H + MeCN]+.
High resolution calculated for IrC46H38O3P2: [M + H]+ 893.19199,
found 893.19242.
∫
Preparation of Ru(C CC6H4Me-4)(dppe)Cp* (4b)
∫
Preparation of Ni(C CC6H5)(PPh3)Cp (6a)
Complex 4b was prepared (63 mg, 56%) from 1b and
RuCl(dppe)Cp* in a manner identical to that described for 4a,
and characterised by comparison of spectroscopic data with that
reported elsewhere.31
A solution of NiBr(PPh3)Cp (100 mg, 0.21 mmol) in THF (10 mL),
was treated with 1a (120 mg, 0.21 mmol) and the mixture allowed
to stir at ambient temperature in the dark, the progress of the
reaction being monitored by TLC (hexane–acetone, 8 : 2) and
by 31P NMR [34.2 ppm for AuBr(PPh3)]. The solution colour
became pale brown after 1 h. After 4 h, the solution was distinctly
green. After stirring for 6 h, the reaction was adjudged complete
and the mixture was taken to dryness, followed by purification
by preparative TLC. A green band was isolated, which was
recrystallised (chloroform/MeOH) to afford green crystals of 6a
2
∫
Formation of Ru(C CC6F5)(g -O2)(PPh3)Cp* (4c)
A mixture of RuCl(PPh3)2Cp* (50 mg, 0.063 mmol) and 1c
(86.6 mg, 0.127 mmol) was heated in refluxing benzene (13 mL)
for 2.5 h to give a red-brown solution. Conventional work-up
gave numerous unidentified products, appearing as multi-coloured
bands on preparative TLC plates, together with AuCl(PPh3)
(5 mg). One yellow band afforded yellow crystals (from hexane)
-1
-1
1
∫
(55 mg, 53%). IR (CH2Cl2) n/cm : (C C) 2097 cm . H NMR
∫
d/ppm: 5.25 (s, 5H, Cp), 6.64 (d, 2H, phenyl C2H at CPh), 6.91
(1.1 mg, 2.4%), identified by a single-crystal X-ray diffraction
(t, 1H, C4H), 6.93 (m, 2H, C3H), 7.38 (m, 9H, PPh3), 7.74 (m, 6H,
PPh3). 31P NMR d/ppm: 41.8 (s, PPh3). 13C NMR d/ppm: 85.8 (d,
2JPC = 50 Hz, Ca), 92.5 (d, 3JPC = 2 Hz, Cp), 119.7 (d, 3JPC = 2 Hz,
2
∫
structure determination as Ru(C CC6F5)(h -O2)(PPh3)Cp* (4c).
The small amount obtained precluded further characterisation.
3
Cb), 124.5 (C4), 127.2 (C3), 128.0 (C1), 128.1 (d, JPC = 10 Hz,
Cm), 130.1 (d, 4JPC = 2 Hz, Cp), 130.9 (C2), 133.8 (d, 2JPC = 10 Hz,
Co), 134.0 (d, 2JPC = 49 Hz, Ci). ES-MS: m/z 995 [2M + Na]+, 509
2
∫
Preparation of Ir(C CC6H5)(g -O2)(CO)(PPh3)2 (5a)
A suspension of IrCl(CO)(PPh3)2 (100 mg, 0.13 mmol) and 1a
(73 mg, 0.13 mmol) were stirred at room temperature in THF
(12 mL) for ca. 6 h to give an orange-brown solution. The progress
of the reaction was monitored by TLC and 31P NMR [26.0 for
+
+
+
∫
[M + Na] , 486 [M] , 385 [M - C CPh] .
∫
Preparation of Ni(C CC6H4Me)(PPh3)Cp (6b)
∫
IrCl(CO)(PPh3)2 and 25.2 ppm for Ir(C CC6H5)(CO)(PPh3)2].
The modestly air- and light-sensitive green complex 6b was
prepared (44 mg, 42%) from 1b and NiBr(PPh3)Cp using the
When the reaction was adjudged complete, 7 mL of the solvent
was removed to give a cloudy brown solution. Acetone (5 mL)
was added to the solution and the mixture stirred for 10 min
followed by filtration to give a yellow solid that was recrystallised
-1
1
∫
method described for 6a. IR (CH2Cl2) n/cm : (C C) 2100. H
NMR d/ppm: 2.17 (s, 3H, CH3), 5.25 (s, 5H, Cp), 6.56 (d, 2H,
tolyl C2H), 6.74 (d, 2H, C3H), 7.40 (m, 9H, PPh3), 7.76 (m, 6H,
PPh3). 31P NMR d/ppm: 41.7 (s, PPh3). 13C NMR d/ppm: 21.2
(CH3), 83.5 (d, 2JPC = 50 Hz, Ca), 92.6 (d, 3JPC = 2 Hz, Cp), 119.7
(d, 3JPC = 2 Hz, Cb), 125.2 (C1), 128.0 (C3), 128.1 (d, 3JPC = 10 Hz,
(CHCl3/hexane) to afford small pale yellow crystals of 5a (71 mg,
-1
∫
∫
62%). IR (CH2Cl2) n/cm : (C C) 2134; (C O) 2005, (O–O) 883.
1H NMR d/cm-1: 2.23 (s, 3H, Me), 6.24 (d, 2H, JHH = 8 Hz,
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 610–620 | 617
©

View Article Online
Cm), 130.1 (d, 4JPC = 2 Hz, Cp), 130.7 (C2), 133.9 (d, 2JPC = 10 Hz,
Preparation of trans-Pt(C CC6H4Me-4)2(PMe3)2 (8b)
∫
2
Co), 134.0 (d, JPC = 47 Hz, Ci), 134.1 (C4). ES-MS: m/z 501
Complex 8b was prepared from 1b (275 mg, 0.48 mmol) and
PtCl2(PMe3)2 and isolated as pale yellow-green crystals (93 mg,
[M + 1]+. Found: C 76.7, H 5.5%. C32H27PNi requires: C 76.7,
H 5.5%.
-1
1
∫
67%). IR (nujol) n/cm : (C C) 2108. H NMR d/ppm: 1.77 (dd,
4
3
2JPH, JPH~4 Hz, and Pt satellites, JPt–H~30 Hz, PMe3), 1.80 (dd,
∫
Preparation of trans-Pt(C CC6H5)2(PPh3)2 (7a)
3JPt–H~30 Hz), 2.29 (s, 6H, Me), 7.03 (d, JHH = 8 Hz, C2H of
1
tolyl), 7.23 (d, JHH = 8 Hz, C3H). 31P{ H} NMR d/ppm: -19.4
To a stirred aliquot of MeOH (15 mL), cis-PtCl2(PPh3)2 (141 mg,
0.18 mmol) and 1a (200 mg, 0.36 mmol) were added to form
a pale yellow suspension. The reaction mixture was allowed
to stir for ca. 15 h, after which time it was filtered and the
precipitate collected and washed with acetone to give a yellow
1
(s + d, 1JPtP = 2310 Hz, PMe3). 13C{ H} NMR d/ppm: 15.4 (dd,
2
2JCP,4JCP~20 Hz, and Pt satellites, JPt–C~83 Hz, PMe3), 21.3 (s,
2
Me), 106.0 (t, JCP = 15 Hz, Ca), 108.4 (Cb), 125.2 (C1), 128.6
(C3), 130.9 (C2), 135.0 (C4). Found: C 49.3, H 5.6%. C24H32P2Pt
requires: C 49.9, H 5.6%. ES-MS: m/z 1177 [2M + Na]+, 632
[M + Na + MeOH]+, 578 [M + H]+. High resolution calculated
for PtP2C24H33: [M + H]+ 578.16997, found 578.17067.
solid, which was recrystallised (CH2Cl2/hexane) to afford pale
-1
∫
yellow crystals of 7a (86 mg, 59%). IR (nujol) n/cm : (C C)
2107. 1H NMR d/ppm: 6.28 (m, 4H, phenyl C2H at CCPh), 6.89
(m, 2H, C4H), 6.91 (m, 4H, C3H), 7.37 (m, 18H, PPh3), 7.81
1
(m, 12H, PPh3). 1P{ H} NMR (CDCl3, 80.96 MHz) d/ppm: 19.7
Isolation of Au(PMe3)2[PF6] (9)
(s + d, JPtP = 2640 Hz, PPh3). 13C{ H} NMR d/ppm: 109.7 (t,
1
1
2JCP~16 Hz, Ca), 113.2 (Cb), 124.5 (C4), 127.0 (C3), 127.8 (dd,
A suspension of PtCl2(PMe3)2 (200 mg, 0.48 mmol), 1a (130 mg,
0.23 mmol) and NH4PF6 (78 mg, 0.48 mmol) in MeOH (15 mL)
was allowed to stir at rt for ca. 8 h to give a white precipitate,
which was collected by filtration, washed with a small quantity
of cold MeOH (3 mL) followed by hexane (3 mL) and dried
in vacuo. Crystallisation of the precipitate from MeCN/MeOH
gave white crystals of 9 (14 mg, 0.028 mmol, 12%) suitable for
3JCP/ JCP~5 Hz, Cm), 128.5 (C1), 130.8 (C2), 130.1 (Cp), 131.4
5
(dd, 1JCP/ JCP~29 Hz Ci), 135.1 (dd, 2JCP/ JCP~5 Hz, Co). Found:
C 68.0, H 4.4%. C52H40P2Pt requires: C 67.8, H 4.4%. ES-MS:
m/z 922 [M + H]+, 944 [M + Na]+. High resolution calculated for
PtC52H41P2: [M + H]+ 922.23257, found 922.23318, calculated for
PtC52H40P2Na: [M + Na]+ 944.21452, found 944.21662.
3
4
X-ray crystallography. 1H NMR d/ppm: 1.70. 31P{ H} NMR
1
d/ppm: 5.0 (s), -144.1 (septet, JPF = 710 Hz). 13C{ H} NMR
1
∫
Preparation of trans-Pt(C CC6H4Me)2(PPh3)2 (7b)
d/ppm: 16.4 (br). ES-MS: m/z 721 [2M + Na]+, 349 [M]+
C6H18AuP2 = [M]+. High resolution calculated for C6H18AuP2:
[M]+ 349.05439, found 349.05424.
A reaction similar to that described for 7a between cis-
PtCl2(PPh3)2 (200 mg, 0.25 mmol) and 1b (291 mg, 0.51 mmol)
gave 7b as a pale yellow precipitate, which was recrystallised
(CH2Cl2/MeOH) to afford pale yellow crystals (83 mg, 35%). IR
(nujol) n/cm : (C C) 2106. H NMR d/ppm: 2.17 (s, 6H, Me),
6.16 (d, JHH~7 Hz, C6H4), 6.70 (d, JHH~7 Hz, C6H4), 7.36 (m, 18H,
∫
Preparation of {Cu(C CC6H5)}n (10a)
-1
1
∫
An aliquot of THF (25 mL) was rapidly stirred and treated with
CuI (100 mg, 0.50 mmol) and 1a (280 mg, 0.50 mmol) to form a
white suspension, which gradually changed to yellow after ca. 2 h.
The reaction was allowed to stir for ca. 24 h to ensure complete
reaction. The yellow suspension was filtered and the solid was
1
1
PPh3), 7.80 (m, 12H, PPh3). P{ H} NMR d/ppm: 19.7 (s + d,
1JPtP = 2660 Hz, PPh3). 13C{ H} NMR d/ppm: 21.2 (Me), 127.7
1
(dd, 3JCP, 5JCP~5 Hz, Cm), 127.9 (C3), 130.1 (C2), 130.8 (Cp), 131.9
1
3
2
4
(dd, JCP, JCP~29 Hz, Ci), 135.1 (dd, JCP, JCP~5 Hz Co), other
13C peaks were not observed due to poor solubility. Found: C 68.8,
H 4.6%. C54H44P2Pt requires: C 68.3, H 4.7%. ES-MS: m/z 950
[M + H]+, 972 [M + Na]+, 982 [M + H + MeOH]+. High resolution
calculated for 194PtC54H45P2: [M]+ 949.256611, found 949.26387.
washed with hexane (5 mL) to give a bright yellow solid (71 mg,
-1
∫
∫
86%) identified as {Cu(C CC6H5)}n 10a. IR (KBr) n/cm : (C C)
1940 (vw), 1481 (m), 742 (s), 679 (s), 520 (m), 511 (m).73 Found: C
58.1, H 3.1%. C8H5Cu requires: C 58.4, H 3.0%.
∫
Preparation of {Cu(C CC6H4Me-4)}n (10b)
∫
Preparation of trans-Pt(C CC6H5)2(PMe3)2 (8a)
A stirred suspension of CuI (200 mg, 1.05 mmol) in THF (60 mL)
was treated with 1b (600 mg, 1.05 mmol) to form a white
suspension, which gradually changed to yellow after ca. 2 h. Using
a similar work-up procedure as described for 10a, a yellow solid
To a stirred aliquot of MeOH (15 mL), trans-PtCl2(PMe3)2
(100 mg, 0.24 mmol) and 1a (269 mg, 0.48 mmol) were added
under nitrogen to afford a pale green suspension, which was stirred
at rt for ca. 15 h, filtered and washed with cold MeOH (3 mL)
∫
(175 mg, 94%) was isolated and identified as {Cu(C CC6H4Me-
and hexane (3 mL), and recrystallised (CHCl3/MeOH) to afford
-1
-1
∫
4)}n (10b). IR (KBr) n/cm : (C C) 1937 (w), 1504 (s), 808 (s),
∫
pale yellow crystals of 8a (99 mg, 73%). IR (nujol) n/cm : (C C)
2108. 1H NMR d/ppm: 1.77 (dd, 2JPH, 4JPH~4 Hz, and Pt satellites,
3JPt–H~30 Hz, PMe3), 1.80 (dd, 3JPt–H~30 Hz), 2.29 (s, 6H, Me), 7.03
526 (m), 520 (m). Found: C 63.6, H 4.1%. C9H7Cu requires: C
60.5, H 3.9%.
(d, JHH = 8 Hz, C2H of tolyl), 7.23 (d, JHH = 8 Hz, C3H). 31P{ H}
1
NMR d/ppm: -19.4 (s + d, 1JPtP = 2300 Hz, PMe3). 13C{ H} NMR
1
Structure determinations†
d/ppm: 15.3 (dd, 2JCP,4JCP~20 Hz, and Pt satellites, 2JPt–C~81 Hz,
2
PMe3), 107.2 (t, JCP = 15 Hz, Ca), 108.5 (Cb), 125.3 (C4), 127.9
Single-crystal X-ray data were collected using an Oxford Diffrac-
tion Xcalibur CCD (11), Rigaku R-AXIS Spider IP (2b and 5b),
Bruker Smart CCD 1 K (6b and 8b) and 6 K (4b, 7a, 7b and
9) diffractometers at low temperature and using monochromatic
(C3), 128.2 (C1), 130.9 (C2). Found: C 47.1, H 5.1%. C24H32P2Pt
requires: C 48.1, H 5.1%. ES-MS: m/z 1162 [2M + Na]+;
550 [M + H]+.
618 | Dalton Trans., 2009, 610–620
This journal is
The Royal Society of Chemistry 2009
©

View Article Online
˚
19, 1814; (n) G. R. Clark, S. V. Hoskins and W. R. Roper, J. Organomet.
Chem., 1982, 234, C9; (o) M. A. Gallop, T. C. Jones, C. E. F. Rickard
and W. R. Roper, J. Chem. Soc., Chem. Commun., 1984, 1002.
6 For a discussion of the hazards associated with the use of mercuric
acetylides see: R. D. Dewhurst, A. F. Hill and M. K. Smith,
Organometallics, 2006, 25, 2388.
7 (a) M. I. Bruce, O. M. Abu Salah, R. E. Davis and N. V. Ragavan,
J. Organomet. Chem., 1974, 64, C48; (b) O. M. Abu Salah and M. I.
Bruce, J. Chem. Soc., Chem. Commun., 1972, 858; (c) O. M. Abu Salah
and M. I. Bruce, J. Chem. Soc., Dalton Trans., 1975, 2311; (d) O. M.
Abu Salah and M. I. Bruce, J. Chem. Soc., Dalton Trans., 1974, 2302;
(e) O. M. Abu Salah and M. I. Bruce, Aust. J. Chem., 1976, 29, 531;
(f) M. I. Bruce, N. N. Zaitseva, B. W. Skelton, N. Somers and A. H.
White, Aust. J. Chem., 2003, 56, 509.
MoKa radiation, l = 0.71073 A. All structures were solved by
direct methods and refined by full matrix least squares refinement
on F2. Anisotropic displacement parameters were refined for
the non-hydrogen atoms, excepting the disordered ones in the
structures 5b and 9; hydrogen atom treatment followed a riding
∫
model. The C CC6H4Me-4 fragment of molecule 5b is disordered
over two equally occupied positions, which correspond to two
different directions of the flexing in the alkyne moiety. The
inclinations of the planar aryl rings are also slightly different.
The disorder does not affect the geometry of rest of the molecule.
Neutral atom complex scattering factors were employed within
the SHELXL-97 program.74 Pertinent results are given in the
tables and figures, the latter showing non-hydrogen atoms with
50% probability amplitude displacement ellipsoids.
8 (a) K. Sonogashira, T. Yatake, Y. Tohda, S. Takahashi and N. Hagihara,
J. Chem. Soc., Chem. Commun., 1977, 291; (b) K. Sonogashira, Y.
Fujikura, T. Yatake, N. Toyoshima, S. Takahashi and N. Hagihara,
J. Organomet. Chem., 1978, 145, 101.
9 M. I. Bruce, M. G. Humphrey, J. G. Matisons, S. K. Roy and A. G.
Swincer, Aust. J. Chem., 1984, 37, 1955.
Acknowledgements
10 O. M. Abu Salah and M. I. Bruce, Aust. J. Chem., 1976, 29, 73.
11 (a) O. M. Abu Salah and M. I. Bruce, Aust. J. Chem., 1977, 30, 2639;
(b) D. Miguel and V. Riera, J. Organomet. Chem., 1985, 293, 379.
12 (a) E. Jime´nez-Nu´n˜ez and A. M. Echavarren, Chem. Commun., 2007,
333; (b) A. S. K. Hashmi and G. J. Hutchings, Angew. Chem., Int. Ed.,
2006, 45, 7896; (c) A. S. K. Hashmi, Angew. Chem., Int. Ed., 2005, 44,
6990; (d) M. Haruta, Nature, 2005, 437, 1098.
13 (a) M. Contel, M. Stol, M. A. Casado, G. P. M. van Klink, D. D. Ellis,
A. L. Spek and G. van Koten, Organometallics, 2002, 21, 4556; (b) M.
Robitzer, I. Bouama¨ıed, C. Sirlin, P. A. Chase, G. van Koten and M.
Pfeffer, Organometallics, 2005, 24, 1756; (c) M. Stol, D. J. M. Snelders,
H. Kooijman, A. L. Spek, G. P. M. van Klink and G. van Koten, Dalton
Trans., 2007, 2589.
14 C.-L. Chan, K.-L. Cheung, W. H. Lam, E. C.-C. Cheng, N. Zhu,
S. W.-K. Choi and V. W.-W. Yam, Chem.–Asian J., 2006, 1, 273.
15 M. Ferrer, L. Rodr´ıguez, O. Russell, J. C. Lima, P. Go´mez-Sal and A.
Mart´ın, Organometallics, 2004, 23, 5096.
16 M. I. Bruce, M. E. Smith, N. N. Zaitseva, B. W. Skelton and A. H.
White, J. Organomet. Chem., 2003, 670, 170.
17 (a) M. I. Bruce, B. W. Skelton, A. H. White and N. N. Zaitseva,
J. Organomet. Chem., 2003, 683, 398; (b) M. I. Bruce, P. A. Humphrey,
G. Melino, B. W. Skelton, A. H. White and N. N. Zaitseva, Inorg. Chim.
Acta, 2005, 358, 1453; (c) A. B. Antonova, M. I. Bruce, B. G. Ellis, M.
Gaudio, P. A. Humphrey, M. Jevric, G. Melino, B. K. Nicholson, G. J.
Perkins, B. W. Skelton, B. Stapleton, A. H. White and N. N. Zaitseva,
Chem. Commun., 2004, 960.
18 M. I. Bruce, E. Horn, J. G. Matisons and M. R. Snow, Aust. J. Chem.,
1984, 37, 1163.
19 X. L. R. Fontaine, S. J. Higgins, C. R. Langrick and B. L. Shaw, J. Chem.
Soc., Dalton Trans., 1987, 777.
We gratefully acknowledge funding from the EPSRC in the
form of a Visiting Fellowship (MIB) and research grants (PJL,
JAKH). WMK gratefully acknowledges funding from the Human
Resources Development in Science and Technology Programme,
Ministry of Science, Technology and Innovation, Malaysia.
References
1 (a) L. Hegedus, Transition Metals in the Synthesis of Complex Organic
Molecules, University Science Books, Mill Valley, California, 1994;
(b) C. Elschenbroich, Organometallics, Wiley-VCH, Weinheim,
Germany, 3rd edn, 2006.
2 (a) F. Diederich and P. J. Stang, Metal-Catalysed Cross-Coupling
Reactions, Wiley-VCH, Weinheim, Germany, 1998; (b) E.-I. Negishi
and A. De Meijere, Handbook of Organopalladium Chemistry for
Organic Synthesis, Wiley, New York, 2002; (c) L. Ku¨rti and B.
Czako´, Strategic Applications of Named Reactions in Organic Synthesis:
Background and Detailed Mechanisms, Elsevier, Oxford, 2005; (d) F.
Chinchilla and C. Na´jera, Chem. Rev., 2007, 107, 874; (e) N. Miyaura
and A. Suzuki, Chem. Rev., 1995, 95, 2457; (f) I. P. Beletskaya and A. V.
Cheprakov, Coord. Chem. Rev., 2004, 248, 2337; (g) K. Sonogashira, Y.
Tohda and N. Hagihara, Tetrahedron Lett., 1975, 4467; (h) D. Milstein
and J. K. Stille, J. Am. Chem. Soc., 1979, 101, 4992; (i) J. Louie and J. F.
Hartwig, J. Am. Chem. Soc., 1995, 117, 11598; (j) N. Miyaura and A.
Suzuki, J. Chem. Soc., Chem. Commun., 1979, 866; (k) S. Baba and E.
Negishi, J. Am. Chem. Soc., 1976, 98, 6729.
20 (a) R. J. Cross and M. F. Davidson, J. Chem. Soc., Dalton Trans., 1986,
411; (b) R. J. Cross, M. F. Davidson and A. J. McLennan, J. Organomet.
Chem., 1984, 265, C37.
21 (a) M. I. Bruce, B. C. Hall, B. W. Skelton, M. E. Smith and A. H. White,
J. Chem. Soc., Dalton Trans., 2002, 995; (b) M. I. Bruce, N. N. Zaitseva,
P. J. Low, B. W. Skelton and A. H. White, J. Organomet. Chem., 2006,
691, 4273.
22 (a) C.-M. Che, H.-Y. Chao, V. M. Miskowski, Y. Li and K.-K. Cheung,
J. Am. Chem. Soc., 2001, 123, 4985; (b) W. Lu, H.-F. Xiang, N. Zhu
and C.-M. Che, Organometallics, 2002, 21, 2343; (c) W. Lu, N. Zhu and
C.-M. Che, J. Organomet. Chem., 2003, 670, 11.
23 (a) P. J. Low and M. I. Bruce, Adv. Organomet. Chem., 2002, 48, 71;
(b) M. I. Bruce and P. J. Low, Adv. Organomet. Chem., 2004, 50, 179.
24 M. I. Bruce and R. C. Wallis, Aust. J. Chem., 1979, 32, 1471.
25 C. Bitcon and M. W. Whiteley, J. Organomet. Chem., 1987, 336, 385.
26 (a) For a representative selection of recent references see: C. E. Powell
and M. G. Humphrey, Coord. Chem. Rev., 2004, 248, 725; (b) N. J. Long
and C. K. Williams, Angew. Chem., Int. Ed., 2003, 42, 2586; (c) M. I.
Bruce, K. Costuas, B. G. Ellis, J.-F. Halet, P. J. Low, B. Moubaraki,
K. S. Murray, N. Oudda¨ı, G. J. Perkins, B. W. Skelton and A. H. White,
Organometallics, 2007, 26, 3735; (d) M. I. Bruce, K. Costuas, J.-F.
Halet, K. A. Kramarczuk, P. J. Low, B. K. Nicholson, G. J. Perkins,
R. L. Roberts, B. W. Skelton, M. E. Smith and A. H. White, Dalton
Trans., 2007, 5387; (e) K. Costuas, F. Paul, L. Toupet, J.-F. Halet and
C. Lapinte, Organometallics, 2004, 23, 2053; (f) F. Paul, L. Toupet, J.-Y.
3 B. Cetinkaya, M. F. Lappert, J. McMeeking and D. E. Palmer, J. Chem.
Soc., Dalton Trans., 1973, 1202.
4 (a) L. Medei, L. Orian, O. V. Semeikin, M. G. Peterleitner, N. A.
Ustynyuk, S. Santi, C. Durante, A. Ricci and C. Lo Sterzo, Eur. J. Inorg.
Chem., 2006, 2582; (b) M. S. Khan, S. J. Davies, A. K. Kakkar,
D. Schwartz, B. Lin, B. F. G. Johnson and J. Lewis, J. Organomet.
Chem., 1992, 424, 87; (c) M. S. Khan, A. K. Kakkar, S. L. Ingham,
P. R. Raithby, J. Lewis, B. Spencer, F. Wittmann and R. H. Friend,
J. Organomet. Chem., 1994, 472, 247; (d) S. J. Davies, B. F. G. Johnson,
J. Lewis and P. R. Raithby, J. Organomet. Chem., 1991, 414, C51.
5 (a) R. J. Cross and M. F. Davidson, Inorg. Chim. Acta, 1985, 97, L35;
(b) A. F. Hill and R. P. Melling, J. Organomet. Chem., 1990, 396,
C22; (c) R. D. Dewhurst, A. F. Hill, A. D. Rae and A. C. Willis,
Organometallics, 2005, 24, 4703; (d) J. P. Collman and J. W. Kang,
J. Am. Chem. Soc., 1967, 89, 844; (e) A. F. Hill and J. D. E. T. Wilton-
Ely, Organometallics, 1997, 16, 4517; (f) R. B. Bedford, A. F. Hill, A. R.
Thompsett, A. J. P. White and D. J. Williams, Chem. Commun., 1996,
1059; (g) G. B. Deacon and D. L. Wilkinson, Inorg. Chim. Acta, 1988,
142, 155; (h) G. B. Deacon and A. J. Koplick, J. Organomet. Chem.,
1978, 146, C43; (i) G. B. Deacon, A. J. Koplick, W. D. Raverty and
D. G. Vince, J. Organomet. Chem., 1979, 182, 121; (j) G. B. Deacon, A. J.
Koplick and T. D. Tuong, Aust. J. Chem., 1982, 35, 941;(k) G. B. Deacon
and R. H. Newham, Aust. J. Chem., 1985, 38, 1757; (l) G. B. Deacon, S.
Nickel, P. MacKinnon and E. R. T. Tiekink, Aust. J. Chem., 1990, 43,
1245; (m) G. Lin, R. McDonald and J. Takats, Organometallics, 2000,
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 610–620 | 619
©

View Article Online
The´pot, K. Costuas, J.-F. Halet and C. Lapinte, Organometallics, 2005,
24, 5464; (g) M. A. Fox, B. Le Guennic, R. L. Roberts, T. E. Baines,
D. S. Yufit, D. Albesa-Jove´, F. Hartl, J. A. K. Howard and P. J. Low,
J. Am. Chem. Soc., 2008, 130, 3566.
51 M. H. Garcia, M. P. Robalo, A. R. Dias, M. T. Duarte, W. Wenseleers,
G. Aerts, E. Goovaerts, M. P. Cifuentes, S. Hurst, M. G. Humphrey,
M. Samoc and B. Luther-Davis, Organometallics, 2002, 21, 2107.
52 C. J. McAdam, A. R. Manning, B. H. Robinson and J. Simpson, Inorg.
Chim. Acta, 2005, 358, 1673.
27 M. I. Bruce, Chem. Rev., 1991, 91, 197.
28 M. I. Bruce, B. C. Hall, B. D. Kelly, P. J. Low, B. W. Skelton and A. H.
White, J. Chem. Soc., Dalton Trans., 1999, 3719.
29 R. C. Bott, G. A. Bowmaker, R. W. Buckley, P. C. Healy and M. C. S.
Perera, Aust. J. Chem., 1999, 52, 271.
30 R. Denis, L. Toupet, F. Paul and C. Lapinte, Organometallics, 2000,
19, 4240.
53 M. P. Gamasa, J. Gimeno, E. Lastra, M. Lanfranchi and A. Tiripicchio,
J. Organomet. Chem., 1991, 405, 333.
54 B. Cordero, V. Go´mez, A. E. Platero-Prats, M. Reve´s, J. Echeverr´ıa, E.
Cremades, F. Barraga´n and S. Alvarez, Dalton Trans., 2008, 2832.
55 F. Paul, B. G. Ellis, M. I. Bruce, L. Toupet, T. Roisnel, K. Costuas, J.-F.
Halet and C. Lapinte, Organometallics, 2006, 25, 649.
31 M. A. Fox, R. L. Roberts, W. M. Khairul, F. Hartl and P. J. Low,
J. Organomet. Chem., 2007, 692, 3277.
32 M. I. Bruce, B. C. Hall, N. N. Zaitseva, B. W. Skelton and A. H. White,
J. Chem. Soc., Dalton Trans., 1998, 1793.
33 C. A. Reed and W. R. Roper, J. Chem. Soc., Dalton Trans., 1973,
1370.
56 G. Jia, W. S. Ng, H. S. Chu, W.-T. Wong, N.-T. Yu and I. D. Williams,
Organometallics, 1999, 18, 3597.
57 (a) H.-H. Wang, L. H. Pignolet, P. E. Reedy, Jr, M. M. Olmstead and
A. L. Balch, Inorg. Chem., 1987, 26, 377; (b) D. G. Ho, R. Ismail, N.
Franco, R. Gao, E. P. Leverich, I. Tsyba, N. N. Ho, R. Bau and M.
Selke, Chem. Commun., 2002, 570; (c) J. A. McGinnety, R. J. Doedens
and J. A. Albers, Inorg. Chem., 1967, 6, 2243.
58 (a) M. S. Weininger, I. F. Taylor, Jr. and E. L. Amma, J. Chem. Soc. D,
1971, 1172; (b) M. S. Weininger, E. A. H. Griffith, C. T. Sears and E. L.
Amma, Inorg. Chim. Acta, 1982, 60, 67.
34 M. I. Bruce, B. C. Hall, P. J. Low, M. E. Smith, B. W. Skelton and A. H.
White, Inorg. Chim. Acta, 300–302, 633.
35 R. H. Walter and B. F. G. Johnson, J. Chem. Soc., Dalton Trans., 1978,
381.
36 C. S. Chin, M. Oh, G. Won, H. Cho and D. Shin, Polyhedron, 1999, 18,
811.
59 S. J. La Placa and J. A. Ibers, J. Am. Chem. Soc., 1965, 87, 2581.
60 L. Vaska, Acc. Chem. Res., 1976, 9, 175.
61 I. R. Whittall, M. G. Humphrey and D. C. R. Hockless, Aust. J. Chem.,
1998, 51, 219.
37 K. Osakada, M. Kimura and J.-C. Choi, J. Organomet. Chem., 2000,
602, 144.
38 C. S. Chin, M. Oh, G. Won, H. Cho and D. Shin, Polyhedron, 1999, 18,
811.
62 (a) C. J. McAdam, A. R. Manning, B. H. Robinson and J. Simpson,
Inorg. Chim. Acta, 2005, 358, 1673; (b) J. F. Gallagher, P. Butler, R. D. A.
Hudon and A. R. Manning, J. Chem. Soc.,Dalton Trans., 2002, 75;
(c) R. H. Naulty, M. P. Cifuentes, M. G. Humphrey, S. Houbrechts, C.
Boutton, A. Persoons, G. A. Heath, D. C. R. Hockless, B. Luther-
Davies and M. Samoc, J. Chem. Soc., Dalton Trans., 1997, 4167;
(d) P. Butler, J. F. Gallagher, A. R. Manning, H. Mueller-Bunz, C. J.
McAdam, J. Simpson and B. H. Robinson, J. Organomet. Chem., 2005,
690, 4545.
63 (a) M. Mayor, C. von Hanisch, H. B. Weber, J. Reichert and D.
Beckmann, Angew. Chem., Int. Ed., 2002, 41, 1183; (b) A. J. Deeming,
G. Hogarth, M. Lee, M. Saha, S. P. Redmond, H. Phetmung and A. G.
Orpen, Inorg. Chim. Acta, 2000, 309, 109; (c) M. Ravera, R. D’Amato
and A. Guerri, J. Organomet. Chem., 2005, 690, 2376; (d) K. Campbell,
R. McDonald, M. J. Ferguson and R. R. Tykwinski, J. Organomet.
Chem., 2003, 683, 379; (e) T. L. Schull, J. G. Kushmerick, C. H.
Patterson, C. George, M. H. Moore, S. K. Pollack and R. Shashidhar,
J. Am. Chem. Soc., 2003, 125, 3202; (f) R. D’Amato, A. Furlani, M.
Colapietro, G. Portalone, M. Casalboni, M. Falconieri and M. V. Russo,
J. Organomet. Chem., 2001, 627, 13.
64 J. Vicente, M.-T. Chicote, M. M. Alvarez-Falco´n and P. G. Jones, Chem.
Commun., 2004, 2658.
65 (a) S. Szafert and J. A. Gladysz, Chem. Rev., 2003, 103, 4175; (b) S.
Szafert and J. A. Gladysz, Chem. Rev., 2006, 106, PR1.
66 M. J. Mays and P. L. Sears, J. Chem. Soc., Dalton Trans., 1973, 1873.
67 M. I. Bruce, C. Hameister, A. G. Swincer and R. C. Wallis, Inorg.
Synth., 1990, 18, 270.
68 M. I. Bruce, B. G. Ellis, P. J. Low, B. W. Skelton and A. H. White,
Organometallics, 2003, 22, 3184.
39 K. Osakada, M. Kimura and J.-C. Choi, J. Organomet. Chem., 2000,
602, 144.
40 M. Itazaki, C. Yoda, Y. Nishihara and K. Osakada, Organometallics,
2004, 23, 5402.
41 A. Antin˜olo, I. Fonseca, A. Ortiz, M. J. Rosales, J. Sanz-Aparicio, P.
Terreros and H. Torrens, Polyhedron, 1999, 18, 959.
42 (a) H. Yamazaki and N. Hagihara, Bull. Chem. Soc. Jpn., 1964, 37,
907; (b) H. Yamazaki, T. Nishido, Y. Matsumoto, S. Sumida and N.
Hagihara, J. Organomet. Chem., 1966, 6, 86; (c) R. Nast, Coord. Chem.
Rev., 1982, 47, 89.
43 U. E. I. Horvarth and H. G. Raubenheimer, Acta Crystallogr., Sect. E:
Struct. Rep. Online, 2007, 63, m567.
44 S. I. Ghazala, F. Paul, L. Toupet, T. Roisnel, P. Hapiot and C. Lapinte,
J. Am. Chem. Soc., 2006, 128, 2463.
45 S. I. Ghazala, N. Gauthier, F. Paul, L. Toupet and C. Lapinte,
Organometallics, 2007, 26, 2308.
46 (a) J. Coumarcel, G. Le Gland, L. Toupet, F. Paul and C. Lapinte,
J. Organomet. Chem., 2003, 670, 108; (b) F. Paul, L. Toupet, J.-Y.
Thepot, K. Costuas, J.-F. Halet and C. Lapinte, Organometallics, 2005,
24, 5464; (c) M. P. Cifuentes, M. G. Humphrey, J. P. Morrall, M. Samoc,
F. Paul, C. Lapinte and T. Roisnel, Organometallics, 2005, 24, 4280.
47 K. Costuas, F. Paul, L. Toupet and C. Lapinte, Organometallics, 2004,
23, 2053.
48 F. Paul, G. da Costa, A. Bondon, N. Gauthier, S. Sinbandhit, L. Toupet,
K. Costuas, J.-F. Halet and C. Lapinte, Organometallics, 2007, 26,
874.
49 (a) K. M.-C. Wong, S. C.-F. Lam, C.-C. Ko, N. Zhu, V. W.-W. Yam, S.
Roue, C. Lapinte, S. Fathallah, K. Costuas, S. Kahlal and J.-F. Halet,
Inorg. Chem., 2003, 42, 7086; (b) Y. Tanaka, T. Ozawa, A. Inagaki
and M. Akita, Dalton Trans., 2007, 928; (c) J. A. Shaw-Taberlet, S.
Sinbandhit, T. Roisnel, J. R. Hamon and C. Lapinte, Organometallics,
2006, 25, 5311; (d) T. Weyland, C. Lapinte, G. Frapper, M. J. Calhorda,
J.-F. Halet and L. Toupet, Organometallics, 1997, 16, 2024.
50 (a) T. Weyland, K. Costuas, L. Toupet, J.-F. Halet and C. Lapinte,
Organometallics, 2000, 19, 4228; (b) F. de Montigny, G. Argouarch,
K. Costuas, J.-F. Halet, T. Roisnel, L. Toupet and C. Lapinte,
Organometallics, 2005, 24, 4558.
69 E. Hernandez and P. Royo, J. Organomet. Chem., 1985, 291, 387.
70 G. B. Kaufmann and L. A. Teter, Inorg. Synth., 1963, 7, 245.
71 D. L. Packett, C. M. Jensen, R. L. Cowan, C. E. Strouse and W. C.
Trogler, Inorg. Chem., 1985, 24, 3578.
72 K. Vrieze, J. P. Collman, C. T. Sears, Jr. and M. Kubota, Inorg. Synth.,
1968, 11, 101.
73 I. A. Garbusova, V. T. Alexanjan, L. A. Leites, I. R. Golding and A. M.
Sladkov, J. Organomet. Chem., 1973, 54, 341.
74 G. M. Sheldrick, SHELXL-97, Program for refinement of crystal
structures, University of Go¨ttingen, Germany, 1997.
620 | Dalton Trans., 2009, 610–620
This journal is
The Royal Society of Chemistry 2009
©