Alkynyl and poly-ynyl derivatives of carbon-tricobalt clusters

Article abstract of DOI:10.1016/j.jorganchem.2006.08.004

A series of alkynyl-tricobalt carbonyl clusters, Co₃(μ₃-C_nR)(μ-dppm)(CO) ₇ [R = Bu^t, Ph, C₆H₄I, C₆H₄C{triple bond, long}CPh, SiMe₃, Fc, Au(PPh

Full text of DOI:10.1016/j.jorganchem.2006.08.004

Journal of Organometallic Chemistry 691 (2006) 4694–4707
www.elsevier.com/locate/jorganchem
Alkynyl and poly-ynyl derivatives of carbon-tricobalt clusters
a,
a
Alla B. Antonova a,b, Michael I. Bruce *, Paul A. Humphrey ,
a
c
a
d
Maryka Gaudio , Brian K. Nicholson , Nancy Scoleri , Brian W. Skelton ,
d
a
Allan H. White , Natasha N. Zaitseva
a
Department of Chemistry, University of Adelaide, Adelaide, SA 5005, Australia
Institute of Chemistry and Chemical Technology, Russian Academy of Sciences, Krasnoyarsk 660049, Russia
b
c
Department of Chemistry, University of Waikato, Hamilton, New Zealand
Chemistry M313, SBBCS, University of Western Australia, Crawley, WA 6009, Australia
d
Received 3 July 2006; received in revised form 2 August 2006; accepted 2 August 2006
Available online 12 August 2006
Abstract
A series of alkynyl-tricobalt carbonyl clusters, Co3(l3-CnR)(l-dppm)(CO)7 [R = But, Ph, C6H4I, C6H4CBCPh, SiMe3, Fc, Au(PPh3)]
containing three, five or seven carbons in the chain, have been prepared by elimination of phosphine–gold(I) halides in reactions between
Co3(l3-CBr)(l-dppm)(CO)7 and Au(CBCR)(PPh3) or between Co3{l3-CCBCAu(PR3)}(l-dppm)(CO)7 (R = Ph, tol) and ICBCR0
(R0 = SiMe3, Fc).The use of poly-substituted arenes or ferrocenes has enabled preparation of the complexes 1,4-{(OC)7(l-dppm)-
Co3(l3-CCBC)}2C6H3X-5 (X = H, Br), 1,3,5-{(OC)7(l-dppm)Co3(l3-CCBC)}3C6H3 and 1,10-{(OC)7(l-dppm)Co3(l3-CCBC)}2Fc0
[Fc0 = Fe(g-C5H4-)2]. The X-ray determined molecular structures of 12 of the complexes are reported.
ꢀ 2006 Published by Elsevier B.V.
Keywords: Carbon-tricobalt cluster; Alkyne; Poly-yne; X-ray structure; Gold
1. Introduction
reactions, or as a component in an appropriate cou-
pling reaction. Notable examples include [{Tp*(OC)2M}
@C@C@C@{M(CO)2Tp*}]2+ and {Tp*(OC)2M}BCCB
C{M0(O)2Tp*} (M, M0 = Mo, W) [5], [{Cp0 (OC)2Mn}-
CCC{Re(NO)(PPh3)Cp*}]+ [6] and {(ButO)3 W}BCCB
C{Re(NO)(PPh3)Cp*} [7]. We and others have consid-
ered an approach to this type of complex using a precur-
sor in which a carbyne ligand, BCR, is attached to a
metal centre. Recent examples have used the Group 6
complexes M(”CR)(CO)2Tp0 [R = halogen, SiMe3; M =
Mo, W; Tp0 = BH(pz)3 (Tp), BH(dmpz)3 (Tp*)] [8] or
cluster-bonded halocarbynes, such as M3(l-CR)(CO)9
(M3 = Ru3(l-H)3 [9], Os3(l-H)3 [9], Co3 [10]).
Current interest in metal complexes containing metal–
ligand centres end-capping carbon chains derives in part
from their potential as models for molecular wires or as
components of molecular-scale electronic devices and mem-
ories and for their non-linear optical properties [1]. Syn-
thetic methods have used synthons derived from alkynes
or poly-ynes, in which the substituent-free carbon chains
are already present. As a result, the majority of known com-
pounds have even-numbered carbon chains [2–4].
The formation of odd-numbered chains is dependent
on methods which have an odd-numbered carbon precur-
sor, either being converted to a Cn chain by subsequent
The trigonal prismatic CCo3 cluster has been known
since the late 1950s [11] and its extensive chemistry has
been reviewed on several occasions [12–17]. Attachment
to unsaturated groups such as alkynes and diynes was
first described in 1970 [18–20]. Common routes to the
*
Corresponding author. Fax: + 61 8 8303 4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0022-328X/$ - see front matter ꢀ 2006 Published by Elsevier B.V.
doi:10.1016/j.jorganchem.2006.08.004

A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
4695
formation of the carbyne–C(sp) bond include the Cadiot-
Chodkiewicz, Sonogashira and related reactions [19]. In
some instances, appropriate Grignard or Lewis-acid
(AlCl3)-induced coupling reactions between alkynes and
Co3(l3-CBr)(CO)9 have been employed. It was early
noted that with metal complexes the amine solvent com-
monly used often resulted in competing degradation of
the cluster and conversion to other unwanted cluster
products [19].
tions of the reaction, in which no base is required, would
prevent the formation of unwanted by-products. While
our first accounts concentrated on the formation of carbon
chains end-capped by the Co3 cluster and a second metal-
containing group [10], we have also extended these reac-
tions to the synthesis of a range of Co3 clusters containing
more conventional groups as described below.
2. Results and discussion
Some time ago, we described a modification whereby
reactions of Co3(l3-CBr)(l-dppm)(CO)7 (1), chosen
because the presence of the edge-bridging diphosphine
ligand prevents break-up of the CCo3 cluster, with phos-
phine–gold(I) alkynyls resulted in elimination of
AuBr(PR3) and formation of the C–C bonded product in
high yields [21]. We had reasoned that the presence of the
dppm ligand, bridging one of the Co–Co edges, would
serve to prevent cluster degradation, while the mild condi-
Reactions of Co3(l3-CBr)(l-dppm)(CO)7 (1) [22] with
phosphine–gold(I) alkynyls proceed readily in solvents
such as thf under mild conditions (r.t., hours) (Scheme
1). Conventional work-up involving chromatography on
silica gel affords the alkynyl-tricobaltcarbon clusters in
high yield as dark coloured crystals. To exemplify this
reaction, we have used Au(CBCR)(PPh3), or occasion-
ally the P(tol)3 analogue to improve solubility, which
PPh2
PPh2
Co(CO)2
Co(CO)2
Ph2P
Ph2P
R
(Ph3P)Au
C
C
(OC)2Co
C
C
C
R
(OC)2Co
CBr
- AuBr(PPh3)
Co
Co
(CO)3
(CO)3
R = But (2), Ph (3), SiMe3 (4), Fc (5)
(1)
C6H4
C
C
Ph (9)
Scheme 1.
PPh2
Co(CO)2
PPh2
Co(CO)2
NaOMe,
then AuCl(PPh3)
Ph2P
Ph2P
(OC)2Co
(OC)2Co
C
C
C
R
C
C
C
Au(PPh3)
Co
Co
(CO)3
(CO)3
(4)
(6)
1,4-I2C6H4
Ph2P
(OC)2Co
PPh2
Co(CO)2
PPh2
Co(CO)2
PPh2
Ph2P
(OC)2Co
Ph2P
C H I-4 +
(OC)2Co
6 4
C
C
C
Co(CO)2
C
C
C
C
C
C
Co
(CO)3
Co
Co
(CO)3
(CO)3
(7)
(8)
Scheme 2.

4696
A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
has
allowed
the
complexes
Co3(l3-CCBCR)-
PPh2
Co(CO)2
(l-dppm)(CO)7 to be obtained [R = But (2, 47%), Ph
(3, 91%), SiMe3 (4, 86%), Fc (5, 91%)]. The co-product
AuBr(PR03) (R0 = Ph, tol) can be easily recovered and
recycled. The IR spectra of these complexes contain
weak m(CBC) bands at ca. 2130 cmꢀ1 and medium to
Ph2P
(OC)2Co
Co(CO)3
C
strong m(CO) absorptions between 2061 and 1966 cmꢀ1
.
PPh2
Co(CO)2
C
C
In addition to common signals at d 3.44 and 4.49 and
between d 6.5 and 8.0 arising from the dppm ligand,
the H NMR spectra contain other resonances character-
Ph2P
1
(OC)2Co
C
C
C
istic of the R groups present. Limited solubility restricted
the availability of 13C NMR spectra, but in 2, signals at
d 101.14 and 121.95 can be assigned to two carbons of
the C3 moiety. That of the carbyne carbon, attached to
three cobalt atoms, is broadened by interaction with
the 59Co quadrupole and is not resolved in all spectra
[23,24]. The 31P NMR spectra contain a single resonance
at d ca. 35. The formulations of these complexes are con-
firmed by elemental analyses and by their electrospray
mass spectra (ES MS), which usually contain molecular
ions or appropriate adduct ions. As described further
below, the molecular structures of 12 of the complexes
have been determined by single-crystal X-ray diffraction
studies.
Co
C
C
(CO)3
C
(CO)2
Co
PPh2
(OC)3Co
Co
(CO)2
PPh2
(10)
PPh2
Co(CO)2
Br
Ph2P
(OC)2Co
C
C
C
The elimination reaction also proceeds between phos-
phine–gold(I) derivatives of the alkynyl-tricobalt cluster
and appropriate C(sp or sp2)-I bonds. Thus, the reaction
between Co3{l3-CCBCAu(PPh3)}(l-dppm)(CO)7 (6),
itself prepared from the SiMe3 derivative 4 and AuCl(PPh3)
in the presence of sodium methoxide, and 1,4-I2C6H4 affor-
ded two complexes which were characterised as Co3(l3-
CCBCC6H4I-4)(l-dppm)(CO)7 (7) which is green, and
orange-brown 1,4-{(OC)7(l-dppm)Co3(l3-CCBC)}2C6H4
(8) (Scheme 2). Similarly, the reaction between
Co
C
C
(CO)3
C
(CO)2
Co
PPh2
(OC)3Co
Co
(CO)2
PPh2
(11)
Au(CBCC6H4CBCPh)(PPh3) and
1 afforded Co3(l3-
In addition to 8, which contains two Co3 clusters
end-capping the organic ligand, we have prepared 1,10-
{(OC)7(l-dppm)Co3(l3-CCBC)}2Fc0 [12, Fc0 = Fe(g-
C5H4-)2] in 96% yield from the related reaction between
1,10-Fc0{CBCAu[P(tol)3]}2 and Co3(l3-CBr)(l-dppm)-
(CO)7. This dark red complex has an IR m(CO) spectrum
similar to those of the other complexes described above,
together with a m(CBC) band at 2122 cmꢀ1. The 1H
NMR spectrum has two multiplets at d 4.40 and 4.53
(4H each) assigned to the C5H4 protons of the ferrocene
nucleus, while the ES MS of a solution containing NaOMe
has [M+Na]+ at m/z 1793.
CCBCC6H4CBCPh)(l-dppm)(CO)7 (9). These complexes
were readily separated by preparative t.l.c. and identified
by elemental analysis and from their ES MS. The other
spectroscopic properties were similar to those found for
the related phenyl complex [22a].
Extension of the reaction to 1,3,5-{(Ph3P)AuCBC}3-
C6H3 enabled preparation of the tris-cluster complex
1,3,5-{(OC)7(l-dppm)Co3(l3-CCBC)}3C6H3 (10) in 50%
yield. This compound has a similar m(CO) spectrum to
the complexes described above, while the 13C NMR spec-
trum contains resonances at d 108.92 and 112.76 from
two of the C3 chain carbons. Further characterisation
results from the ES MS which contains a molecular ion
at m/z 2454, and by an X-ray structural determination
(see below). On one occasion, we isolated and crystallo-
graphically characterised the bis-cluster 1,3-{(OC)7(l-
dppm)Co3(l3-CCBC)}2C6H3Br-5 (11) from an analogous
reaction in which the bromoaryl-diyne 1,3-{(Ph3P)-
AuCBC}2C6H3Br-5 was inadvertently used. Its spectro-
scopic properties were similar to those found for 9, with
the exception of the negative ion ES MS, in which the peak
at a m/z 1741 corresponds to [MꢀH]ꢀ.
PPh2
Co(CO)2
Ph2P
(OC)2Co
Ph2P
(OC)2Co
C
C
C
PPh2
Fe
Co
C
C
C
Co(CO)2
(CO)3
Co
(CO)3
(12)

A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
4697
Related complexes with C5 chains, such as Co3(l3-
CCBCCBCR)(l-dppm)(CO)7 [R = SiMe3, Au(PPh3), Fc]
have been described earlier [10]. Extension to systems con-
taining C7 chains was easily achieved in reactions between
Co3{l3-CCBCCBCAu(PPh3)}(l-dppm)(CO)7 [10] and
ICBCSiMe3 [25] or ICBCFc [26] which gave Co3{l3-
C(CBC)3R}(l-dppm)(CO)7 [R = SiMe3 (13, 54%), Fc
(14, 87%)] and the further conversion of 13 by treatment
with NaOMe and AuCl(PPh3) gave Co3{l3-C(CBC)3-
Au(PPh3)}(l-dppm)(CO)7 (15) in 75% yield (Scheme 3).
The complex Co3{l3-CCBCCBCAu(PPh3)} (l-dppm)-
(CO)7 has been converted to Co3{l3-C(CBC)3Ph}-
(l-dppm)(CO)7 (16) in 60% yield by sequential reactions
with iodine and Au(CBCPh)(PPh3), without isolation of
the presumed intermediate iododiynyl complex Co3(l3-
CCBCCBCI)(l-dppm)(CO)7.
C221
O22
O33
C222
C42
C4
P2
Co2
C0
C212
C2
C211
C1
O21
O31
C3
C43
Co3
C41
Co1
P1
O11
C111
C112
O32
C121
C122
O12
Complexes 13–16 were initially characterised by elemen-
tal microanalyses and from their ES MS. Other spectro-
scopic properties were also in agreement with the
proposed structures. These complexes have similar IR spec-
tra to their shorter chain analogues, although for 14 and
16, two m(CBC) absorptions are found. In the NMR spec-
tra of 13, the SiMe3 group gives rise to a singlet at dH 0.26,
while for 14, resonances at dH 4.28, 4.30 and 4.56 and dC
70.35, 69.76 and 72.35 arise from the Cp and C5H4 rings
of the Fc group. We assign seven resonances found
between d 63.38 and 99.03 in the 13C NMR spectrum to
six of the C7 carbons and the ipso carbons of the Ph groups.
In the 13C NMR spectra of 14 and 15, resonances between
d 57 and 99 are assigned to five of the seven chain carbons,
the Co3C atom again not being observed.
Fig. 1. Plot of a molecule of Co3(l3-CCBCBut)(l-dppm)(CO)7 (2).
common structural feature the Co3(l3-CCBC-)(l-
dppm)(CO)7 fragment (the molecule of 12 is centrosymmet-
ric), as has been found in several other related complexes
described by us [10,27] and others [28–31] on previous
occasions. Atom C(1) is attached to all three metal atoms
of the triangular Co3 cluster, of which one edge [Co(1)–
Co(2)] is bridged by the dppm ligand. In all cases except
2 and 4 (which are isomorphous), the methylene bridge
of the dppm ligand lies ‘endo’ to the pendant alkyne group,
whereas it is ‘exo’ in the two exceptions. Nevertheless, the
ranges encompassed by the various bond distances and
angles extend over many standard deviations (see Table 1),
although it is not evident that any particular structural or
electronic feature can account for the differences.
3. Structural studies
The molecular structures of 12 of the complexes
described above have been determined by single-crystal
X-ray diffraction studies. Figs. 1–12 contain plots of single
molecules of each complex, that of 5 showing the two dif-
ferent conformers found in the unit cell. All contain as a
In some instances, the dppm-bridged Co(1)–Co(2) bond
is significantly different from the other two Co–Co separa-
tions, although when averaged over the present exam-
˚
ples, all distances are identical (2.48 A), with ranges for
PPh2
PPh2
Co(CO)2
Ph2P
Co(CO)2
Ph2P
I
C
C R
(OC)2Co
C
(C
C)2 Au(PPh3)
(OC)2Co
C
(C
C)3 R
Co
(CO)3
Co
(CO)3
(6)
R = SiMe3 (13)
NaOMe,
then AuCl(PPh3)
Au(PPh3) (15)
Fc (14)
I2, then Au(C≡CPh)(PPh3)
Ph (16)
Scheme 3.

4698
A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
Cl(1)
CO(122)
Cl(2)
1222
212
211
1211
1212
CO(22)
1221
305
306
CO(133)
CO(121)
CO(131)
P(12)
CO(21)
304
221
Co(2)
1305
Co(12)
P(2)
1304
CO(33)
10
13
1301
12
301
3
11
Co(13)
2
303
222
0
1303
1122
1302
302
CO(31)
CO(11)
Co(11)
1
Fe(1)
1304’
CO(132)
Co(1)
P(1)
CO(111)
1305’
1303’
111
1112
1111
CO(112)
121
122
CO(32)
1301’
1302’
CO(12)
Fig. 2. Plot of a molecule of Co3(l3-CCBCPh)(l-dppm)(CO)7 (3).
1
CO(222)
CO(22)
2211
2212
CO(221)
221
2305
2222
2304’
CO(33)
102
2305’
2301
222
CO(233)
P(22)
20
2304
Fe(2)
P(2)
2303’
Co(22)
212
23
CO(21)
22
Co(2)
Si
103
2301’
2302
2303
2302’
0
3
2
Co(23)
Co(21)
2122
CO(231)
CO(211)
1
21
CO(31)
Co(1)
P(21)
101
112
116
2112
2111
2121
CO(232)
CO(11)
122
P(1)
121
CO(32)
CO(12)
CO(212)
2
Fig. 4. Plots of molecules 1 and 2 of Co3(l3-CCBCFc)(l-dppm)(CO)7 (5).
Fig. 3. Plot of a molecule of Co3(l3-CCBCSiMe3)(l-dppm)(CO)7 (4).
The carbon chains show the expected alternation of C–C
bond lengths, with C(1)–C(2) ranging between 1.381 and
1.422 A (av. 1.399 A) and C(2)–C(3) being shorter at
˚
˚
˚
˚
˚
Co(1)–Co(2) of between 2.4624 and 2.5144 A and for
1.213 A (av.), range 1.201–1.230 A, consistent with its
being a CBC triple bond. As expected, angles at C(1,2)
are close to linear, averaging 177.2ꢁ (range 174.3–179.8ꢁ)
and 174.7 (range 167.9–179.3ꢁ), respectively. In triyne com-
plexes 11 and 12, separations further along the C7 chain are
consistent with this formulation, with C(4)–C(5) and C(6)–
˚
Co(1,2)–Co(3) of 2.4651 and 2.5085 A. The Co–P bonds
˚
to the dppm ligand average 2.197 A (range 2.177–
˚
2.2154 A). Only in the interactions of the Co3 cluster with
the capping C(1) atom are differences found, with Co(1,2)–
˚
˚
C(1) averaging 1.905 A (range 1.888–1.928 A) and Co(3)–
˚
˚
˚
C(1) averaging 1.937 A (range 1.914–1.978 A), resulting
from the increased electron density at Co(1,2) and
increased back-bonding into the corresponding Co–C
MOs [32].
C(7) triple bonds [1.217, 1.203(4) A in 11, 1.226, 1.209(7) in
12] and C(3)–C(4) and C(5)–C(6) single bonds [1.355,
˚
1.366(4) A in 11, 1.343, 1.358(7) in 12]. In these two exam-
ples, a trend for shorter CBC triple bonds further along the

A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
4699
722
822 CO(71)
CO(81)
CO(91)
Co(9)
CO(22)
212
821
721
P(7)
712
202
Co(7)
212
3
221
Co(8)
CO(33)
P(2)
CO(21)
301
Co(2)
711
2
1
Au
7
201
CO(22)
221
302
CO(93)
P
Co(3)
Co(1)
212
CO(92)
8
0
CO(31)
CO(11)
222
9
P(1)
101
211
P(2)
1
306
CO(32)
CO(21)
CO(31)
305
102
111
121
2
3
301
302
Co(3)
122
304
303
10
CO(32)
CO(12)
112
Co(1)
121
6
512
511
111
5
CO(11)
CO(12)
112
P(5)
4
CO(52)
40
411
Fig. 5. Plot of a molecule of Co3{l3-CCBCAu(PPh3)}(l-dppm)(CO)7 (6).
Co(5)
521
522
Co(6)
CO(42)
CO(41)
CO(51)
CO(61)
212
Fig. 8. Plot of a molecule of 1,3,5-C6H3{CBC-l3-C[Co3(l-dppm)(CO)7]}3
(10).
CO(22)
211
CO(21)
306
301
305
I(304)
CO(22)
212
CO(33)
221
Co(2)
304
303
222
CO(31)
3
Br(303)
0
2
CO(33)
211
CO(21)
1
302
P(2)
Co(1)
P(1)
303
302
Co(2)
Co(3)
CO(31)
10
1
2
3
CO(11)
CO(32)
111
304
301
306
122
121
Co(1)
305
P(1)
122
CO(32)
121
CO(52)
4
112
CO(11)
CO(12)
512
5
111
CO(12)
112
CO(63)
411
6
Co(6)
511
Co(5)
Fig. 6. Plot of a molecule of Co3(l3-CCBCC6H4I-4)(l-dppm)(CO)7 (7).
20
412
CO(51)
Co(4)
CO(61)
P(4)
CO(42)
421
CO(22)
CO(33)
522
CO(41)
422
212
3
221
211
P(2)
CO(21)
CO(31)
Co(2)
Co(3)
0
1
2
302
305
Fig. 9. Plot of a molecule of 1,3,5-C6H3Br{CBC-l3-C[Co3(l-dppm)-
(CO)7]}2 (11).
Co(1)
303
304
301
P(1)
CO(32)
111
4
126
5
502
501
306
CO(11)
Cn chain from the Co3 cluster is evident, while the reverse
occurs for the C–C single bonds. The conformations of
these two C7 chains can be described as a continuous bend,
with total bending at the carbon atoms C(2-7), R, being
19.4ꢁ (for 11) and 23.6ꢁ (for 12). Others have commented
previously about the facile bending of C(sp) chains, the
most probable explanation being found in intermolecular
503
CO(12)
112
504
506
505
Fig. 7. Plot of a molecule of Co3(l3-CCBCC6H4CBCPh-4)(l-dppm)-
(CO)7 (9).

4700
A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
symmetry in their disposition in the cell, the two indepen-
CO(22)
dent molecules of 5 have different conformations of the
Fc group, with the Fe-mid-ring vectors being approxi-
mately parallel and perpendicular to the Co(1)–Co(2) vec-
tor, no doubt imposed by packing requirements of the Ph
and Fc groups therein.
CO(33)
211
P(2)
212
3
CO(21)
305
Fe
304
303
Co(2)
Co(3)
CO(31)
301
302
0
1
2
122
P(1)
CO(32)
Co(1)
4. Experimental
CO(11)
CO(12)
4.1. General
112
All reactions were carried out under dry nitrogen,
although normally no special precautions to exclude air
were taken during subsequent work-up. Common solvents
were dried, distilled under argon and degassed before use.
Separations were carried out by preparative thin-layer
chromatography on glass plates (20 · 20 cm2) coated with
silica gel (Merck, 0.5 mm thick).
Fig. 10. Plot of a molecule of 1,10-Fc0{CBC-l3-C[Co3(l-dppm)(CO)7]}2
(12).
4.2. Instruments
72
CO(22)
211
2
CO(33)
212
3
CO(21)
73
IR spectra were obtained on a Bruker IFS28 FT-IR
spectrometer. Spectra in CH2Cl2 were obtained using a
0.5 mm path-length solution cell with NaCl windows.
Nujol mull spectra were obtained from samples mounted
between NaCl discs. NMR spectra were recorded on a
Varian 2000 instrument (1H at 300.13 MHz, 13C at
75.47 MHz, 31P at 121.503 MHz). Unless otherwise stated,
samples were dissolved in CDCl3 contained in 5 mm sam-
ple tubes. Chemical shifts are given in ppm relative to
222
P(2)
7
6
Si(7)
5
Co(2)
Co(3)
4
71
0
1
CO(31)
CO(11)
Co(1)
122
CO(32)
111
P(1)
121
CO(12)
112
1
internal tetramethylsilane for H and 13C NMR spectra
and external H3PO4 for 31P NMR spectra. Electrospray
mass spectra (ES MS) were obtained from samples dis-
solved in MeOH unless otherwise indicated. Solutions
were injected into a Varian Platform II spectrometer via
a 10 ml injection loop. Nitrogen was used as the drying
and nebulising gas. Chemical aids to ionisation were used
[34]. Elemental analyses were by CMAS, Belmont, Vic.,
Australia.
Fig. 11. Plot of a molecule of Co3{l3-C(CBC)3SiMe3}(l-dppm)(CO)7
(13).
CO(22)
211
212
3
221
76
72
75
73
CO(33)
1
CO(21)
Co(2)
Co(3)
71
7
4.3. Reagents
6
5
CO(31)
4
2
74
0
122
Co(1)
Co3(l3-CBr)(l-dppm)(CO)7 [27], ICBCFc [26], AuCl
(PR3) (R = Ph; tol made similarly) [35], and Au(CBCR0)
(PR3) (R0 = But, Ph, SiMe3, Fc) and {Au(PR3)}2(l-
CBCC6H4CBC) were obtained as previously described
[36,37].
CO(32)
CO(11)
111
CO(12)
112
4.4. Preparation of Au(CBCC6H4CBCPh)(PPh3)
Fig. 12. Plot of a molecule of Co3{l3-C(CBC)3Ph}(l-dppm)(CO)7 (16).
Sodium (30 mg, 1.3 mg atom) was added to a solution
of AuCl(PPh3) (91 mg, 0.184 mmol) in MeOH (28 ml).
After hydrogen evolution had ceased, a solution of
HCBCC6H4CBCPh (37 mg, 0.183 mmol) in MeOH
(2 ml) was added dropwise. After stirring at r.t. for 12 h,
solvent was removed and the residue was extracted with
benzene. Concentration of the extract to 3 ml and diffusion
interactions within the cell and the facile bending modes of
C(sp) chains [33].
Other features of the structures are consistent with the
groups found at the other end of the carbon chain, with
C(3)–X distances [X = Au 1.983(4), C(301) of aromatic
˚
groups 1.405–1.440(5), Si 1.845(6) A]. Despite pseudo-

A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
4701
Table 1
Selected bond parameters for some alkynyl-Co3C complexes
Bond
2
3
4
5a
˚
Distances (A)
Co(1)–Co(2)
Co(1)–Co(3)
Co(2)–Co(3)
Co(1)–P(1)
Co(2)–P(2)
P(1)–C(0)
2.5103(6)
2.5085(4)
2.4989(4)
2.2154(5)
2.2118(4)
1.862(1)
1.858(2)
1.918(2)
1.928(1)
1.978(1)
2.4794(4)
2.4867(5)
2.4831(4)
2.1938(6)
2.2018(6)
1.832(2)
1.830(2)
1.896(2)
1.906(2)
1.932(2)
2.4924(6)
2.4719(5)
2.4651(4)
2.1896(6)
2.1842(6)
1.836(2)
1.832(2)
1.895(2)
1.898(2)
1.943(2)
1.403(3)
1.217(3)
1.824(2) [Si]
2.465, 2.460(1)
2.468, 2.485(1)
2.484, 2.486(1)
2.177, 2.195(2)
2.189, 2.191(2)
1.842, 1.839(7)
1.843, 1.843(7)
1.910, 1.903(6)
1.895, 1.911(6)
1.914, 1.940(8)
1.409, 1.384(10)
1.206, 1.205(10)
1.405, 1.433(10) [C(301)]
P(2)–C(0)
Co(1)–C(1)
Co(2)–C(1)
Co(3)–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–X [X]
1.422(2)
1.225(2)
1.494(2) [C(4)]
1.403(3)
1.209(3)
1.433(3) [C(301)]
Angles (ꢁ)
Co(3)–Co(1)–P(1)
Co(3)–Co(2)–P(2)
P(1)–C(0)–P(2)
Co(1)–C(1)–C(2)
Co(2)–C(1)–C(2)
Co(3)–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–X [X]
153.68(2)
155.67(1)
106.83(7)
137.0(1)
134.1(1)
122.9(1)
146.77(2)
147.3(2)
110.5(1)
139.2(2)
126.0(2)
128.3(2)
175.8(2)
175.9(2) [C(301)]
154.05(2)
155.00(2)
107.3(1)
136.2(2)
134.2(1)
123.1(1)
177.9(2)
174.7(2) [Si]
148.49, 147.14(6)
147.26, 147.88(6)
108.2, 108.9(4)
130.6, 137.8(5)
137.0, 126.4(4)
126.5, 130.6(5)
179.8, 177.1(7)
178.8, 174.1(8) [C(301)]
176.7(2)
177.3(2) [C(4)]
Bond
6b
7b
9c
10d
˚
Distances (A)
Co(1)–Co(2)
Co(1)–Co(3)
Co(2)–Co(3)
Co(1)–P(1)
Co(2)–P(2)
P(1)–C(0)
2.4628(7)
2.4743(8)
2.4982(7)
2.192(1)
2.202(1)
1.825(3)
1.836(6)
1.907(3)
1.910(4)
1.928(4)
1.401(5)
1.213(6)
1.983(4) [Au]
2.4760(5)
2.4804(7)
2.4884(8)
2.194(1)
2.203(1)
1.839(3)
1.849(3)
1.907(3)
1.921(3)
1.934(3)
2.4870(7)
2.4802(7)
2.4801(7)
2.203(1)
2.200(1)
1.824(3)
1.831(4)
1.927(4)
1.888(4)
1.935(4)
2.467, 2.463, 2.484(5)
2.486, 2.469, 2.475(5)
2.505, 2.489, 2.480(5)
2.190, 2.194, 2.200(9)
2.193, 2.205, 2.207(9)
1.84, 1.83, 1.80(3)
1.87, 1.84, 1.84(3)
1.96, 1.95, 1.93(2)
1.88, 1.86, 1.92(3)
1.96, 1.92, 1.98(4)
P(2)–C(0)
Co(1)–C(1)
Co(2)–C(1)
Co(3)–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–X [X]
1.394(4)
1.214(5)
1.436(5) [C(301)]
1.394(5)
1.213(5)
1.434(5) [C(301)]
1.38, 1.41, 1.39(5)
1.24, 1.20, 1.17(5)
1.44, 1.42, 1.43(5) [C(30n)]
Angles (ꢁ)
Co(3)–Co(1)–P(1)
Co(3)–Co(2)–P(2)
P(1)–C(0)–P(2)
Co(1)–C(1)–C(2)
Co(2)–C(1)–C(2)
Co(3)–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–X [X]
148.08(3)
143.48(4)
110.4(2)
133.4(3)
133.5(2)
128.0(3)
177.3(4)
171.3(3) [Au]
145.62(3)
147.66(3)
110.3(2)
136.1(2)
127.8(2)
131.0(2)
175.1(5)
171.4(4) [C(301)]
149.82(3)
148.42(3)
109.2(2)
124.2(3)
138.8(3)
130.9(3)
174.3(4)
167.9(4)
147.1, 146.2, 146.9(2)
146.5, 147.4, 149.5(3)
107, 108. 110(2)
129, 127, 130(2)
140, 139, 139(2)
126, 128, 128(2)
177, 178, 173(3)
178, 179, 175(3)
Bond
11e
12
13f
16g
˚
Distances (A)
Co(1)–Co(2)
Co(1)–Co(3)
Co(2)–Co(3)
Co(1)–P(1)
Co(2)–P(2)
P(1)–C(0)
2.4789, 2.5144(7)
2.4760, 2.4779(7)
2.4654, 2.4728(7)
2.192, 2.211(1)
2.189, 2.186(1)
1.826, 1.836(3)
1.839, 1.829(3)
1.903, 1.893(3)
1.900, 1.895(3)
1.923, 1.951(4)
1.405, 1.405(5)
2.4788(6)
2.4738(6)
2.4695(6)
2.1923(9)
2.1915(9)
1.830(3)
1.838(3)
1.905(3)
1.895(3)
1.930(3)
1.402(4)
2.4624(6)
2.4612(6)
2.4853(7)
2.179(1)
2.210(1)
1.832(3)
1.842(4)
1.903(4)
1.903(4)
1.942(4)
1.381(6)
2.4853(5)
2.4922(5)
2.4855(5)
2.2023(7)
2.2136(7)
1.830(2)
1.839(2)
1.911(2)
1.905(2)
1.937(2)
1.385(3)
P(2)–C(0)
Co(1)–C(1)
Co(2)–C(1)
Co(3)–C(1)
C(1)–C(2)
(continued on next page)

4702
A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
Table 1 (continued)
Bond
11e
12
13f
16g
C(2)–C(3)
C(3)–X
1.210, 1.201(5)
1.431, 1.440(5) [C(301, 305)]
1.209(4)
1.419(4) [C(301)]
1.224(7)
1.343(7) [C(4)]
1.230(3)
1.355(4) [C(4)]
Angles (ꢁ)
Co(3)–Co(1)–P(1)
Co(3)–Co(2)–P(2)
P(1)–C(0)–P(2)
Co(1)–C(1)–C(2)
Co(2)–C(1)–C(2)
Co(3)–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–X
147.28, 149.83(4)
146.61, 152.08(3)
108.8, 110.9(2)
130.6, 134.7(3)
132.7, 133.1(3)
131.3, 125.2(3)
176.5, 178.9(4)
179.3, 178.1(4) [C(301, 305)]
149.97(3)
147.49(3)
108.1(1)
131.2(2)
135.2(2)
128.1(2)
178.2(3)
175.8(3) C(301)]
146.44(4)
148.25(4)
111.8(2)
136.5(3)
130.0(3)
129.0(3)
178.0(4)
173.0(4) [C(4)]
147.47(2)
149.24(2)
109.1(1)
129.1(2)
137.2(2)
127.7(2)
177.6(3)
174.1(3) [C(4)]
a
For 5: Values for two independent molecules.
b
c
˚
For 6: Au–P 2.271(1) A, C(3)–Au–P 175.4(1)ꢁ.
˚
For 7: C(304)–I 2.105(3) A.
d
˚
For 9: C(304)–C(4) 1.431(6), C(4)–C(5) 1.203(6), C(5)–C(501) 1.420(6) A; C(304)–C(4)–C(5) 177.6(5), C(4)–C(5)–C(501) 177.4(5)ꢁ. For 10: Second and
third entries are for second and third clusters involving Co(4–6), P(4,5), C(303, 4–6) and Co(7–9), P(7,8), C(305, 7–9).
e
˚
For 11: Second entries are values for second cluster involving Co(4–6), P(4,5), C(305, 4–6). C(303)–Br 1.895(3) A.
For 13: C(4)–C(5) 1.226(7), C(5)–C(6) 1.358(7), C(6)–C(7) 1.209(7), C(7)–Si 1.845(6) A; C(3)–C(4)–C(5) 175.5(4), C(4)–C(5)–C(6) 175.7(4), C(5)–C(6)–
f
˚
C(7) 178.3(4), C(6)–C(7)–Si 175.9(4)ꢁ.
g
˚
For 16: C(4)–C(5) 1.217(4), C(5)–C(6) 1.366(4), C(6)–C(7) 1.203(4), C(7)–C(71) 1.437(4) A; C(3)–C(4)–C(5) 177.6(3), C(4)–C(5)–C(6) 176.1(3), C(5)–
C(6)–C(7) 176.8(3), C(6)–C(7)–C(71) 178.4(3)ꢁ.
of heptane (3 ml) into the concentrated solution gave light
yellow microcrystalline Au(CBCC6H4CBCPh)(PPh3)
(99.5 mg, 83%), which was washed with hexane and dried.
Anal. Calc. for C34H24AuP (Mw = 660): C, 61.82; H, 3.64.
Found: C, 61.62; H, 3.57%. IR (CH2Cl2): m(CBC)
with CH2Cl2 and separated by preparative t.l.c. (hexane–
acetone 5/1). The major brown band (Rf 0.41) contained
Co3(l3-CCBCBut)(l-dppm)(CO)7 (2) (47 mg, 47%) which
was isolated as dark brown crystals (CH2Cl2/MeOH).
Anal. Calc. for C39H31Co3O7P2 (MW = 850): C, 55.06;
H, 3.65. Found: C, 55.09; H, 3.42%. IR (CH2Cl2, cmꢀ1):
m(CBC) 2131vw; m(CO) 2057s, 2007vs, 1987 (sh), 1966
(sh); (cyclohexane): m(CO) 2061s, 2015vs, 2011vs, 1997m,
1984w, 1976m, 1960w. 1H NMR: d 1.41 (s, 9H, But),
3.49, 4.41 (2 · s, 2 · 1H, dppm), 6.50–8.50 (m, 20H, Ph).
13C NMR: d 30.33 (s, Me), 30.80 (s, C4), 39.94 [t, J(CP)
21.8 Hz, PCH2], 101.14 (s, C3), 121.95 (s, C2), 128.12–
137.49 (m, Ph), 202.43, 209.83, 231.35 (3 · s, br, CO). 31P
NMR: d 33.8 (s, dppm). ES-MS (MeOH, m/z): 850, M+.
1
2114w cmꢀ1. H NMR: d 7.27–7.60 (m, 24H, Ph + C6H4).
31P NMR: d 42.6 (s, PPh3). ES-MS: (positive ion,
MeOH + NaOMe, m/z): 683, [M+Na]+.
4.5. Preparation of 1,3,5-{(Ph3P)AuCBC}3C6H3
A modified literature method [38] was used. NaOMe
(excess) in MeOH (4 ml) was added to a solution of
AuCl(PPh3) (202.7 mg, 0.41 mmol) and 1,3,5-(Me3SiCB
C)3C6H3 (50 mg, 0.137 mmol) in thf/MeOH (30 ml/8 ml)
at 0 ꢁC (ice-bath) and the mixture was allowed to warm
to r.t. After stirring overnight, a white precipitate had sep-
arated from the pale yellow solution. Solvent was removed
and the solid remaining was transferred to a sintered filter
with MeOH (5 ml) and washed with more MeOH and hex-
ane, and dried in air to give 1,3,5-{(Ph3P)AuCBC}3C6H3
4.6.1.2. R = Ph (3). Method A:
A
mixture of
Au(CBCPh)(PPh3) (66 mg, 0.12 mmol), Co3(l3-CBr)(l-
dppm)(CO)7 (100 mg, 0.12 mmol), Pd(PPh3)4 (7 mg,
0.006 mmol) and CuI (2 mg, 0.012 mmol) in thf (7 ml)
was stirred at r.t. for 1 h. After removal of solvent, the res-
idue was taken up in CH2Cl2 and purified by preparative
t.l.c. (acetone–hexane 3/7). The major brown-green band
(Rf 0.69) contained Co3(l3-CCBCPh)(l-dppm)(CO)7 (3)
(93.2 mg, 91%) as dark green crystals (CH2Cl2/MeOH).
Anal. Calc. for C41H27Co3O7P2 Æ 0. 5CH2Cl2 (MW =
870): C, 54.57; H, 3.28. Found: C, 54.73; H, 2.75%. IR
(CH2Cl2, cmꢀ1): m(CBC) 2116vw; m(CO) 2058s, 2009vs,
1989 (sh), 1969 (sh), 1948 (sh). 1H NMR: d 3.44, 4.49
(2 · s, 2 · 1H, dppm), 5.30 (s, CH2Cl2), 7.14–7.59 (m,
25H, Ph). 31P NMR: d 34.2 [s (br), dppm]. ES-MS (positive
ion, MeOH + NaOMe, m/z): 893, [M+Na]+; (negative ion,
MeOH, m/z): 869, [MꢀH]+.
1
(181 mg, 87%) as a pale yellow solid. H NMR: d 7.47–
7.59 (m, Ph). 13C NMR: d 103.62 (CBC), 124.35 (s, Cipso
of C6H3), 18.89–131.44 (m, Ph), 134.20, 134.36 (C6H3).
31P NMR: d 49.3 (s, PPh3).
4.6. Preparation of carbon-tricobalt complexes
4.6.1. Co3(l3-CCBCR)(l-dppm)(CO)7
4.6.1.1. R = But(2). A mixture of Au(CBCBut)(PPh3)
(64 mg, 0.12 mmol), Co3(l3-CBr)(l-dppm)(CO)7 (100 mg,
0.12 mmol), Pd(PPh3)4 (6.2 mg, 0.006 mmol) and CuI
(1 mg, 0.005 mmol) in thf (7 ml) was stirred at r.t. for
2 h. After removal of solvent, the residue was extracted
Method B: When Ag(CBCPh)(PPh3) was used under
the same conditions, 3 was obtained in 55% yield.

A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
4703
4.6.1.3. R = SiMe3 (4). Method A: Pd(PPh3)4 (6 mg,
0.005 mmol) and CuI (1 mg, 0.005 mmol) were added to
4.6.1.5. R = Au(PPh3) (6). A solution containing 4
(100 mg, 0.12 mmol) and AuCl(PPh3) (57 mg, 0.12 mmol)
in thf/MeOH (4/1, 5 ml) was treated with NaOMe [from
Na (6 mg) in MeOH (1 ml)] and the mixture was stirred
at r.t. for 3 h. After removal of solvent under vacuum,
the brown residue was transferred to a sintered filter,
washed with MeOH and hexane and dried. Crystallisation
(CH2Cl2/MeOH) gave Co3{l3-CCBCAu(PPh3)}(l- dppm)-
(CO)7 (6) (130 mg, 90%) as dark red crystals. Anal. Calc.
for C53H37AuCo3O7P3 (MW = 1252): C, 50.80; H, 2.95.
Found: C, 50.65; H, 3.02%. IR (CH2Cl2, cmꢀ1): m(CBC)
2137vw; m(CO) 2053s, 2005vs, 1983 (sh), 1961 (sh); (cyclo-
hexane): m(CO) 2061s, 2015vs, 2011vs, 1997m, 1984w,
1976m, 1960w. 1H NMR: d 3.24, 5.04 (2 · s, 2 · 1H,
dppm), 7.15–7.59(m, 35H, Ph). 31P NMR: d 32.5 [s (br),
dppm], 43.5 [s (br), PPh3]. ES-MS (positive ion, MeOH,
m/z): 1253, [M+H]+; (MeOH + NaOMe, m/z): 1275,
[M+Na]ꢀ.
a
solution of Co3(l3-CBr)(l-dppm)(CO)7 (84.9 mg,
0.1 mmol) and Au(CBCSiMe3)(PPh3) (55.6 mg, 0.1 mmol)
in thf (5 ml) and the mixture was stirred at r.t. for 2 h. After
removal of solvent under reduced pressure, the residue was
dissolved in acetone–hexane (3/7) and run through a silica
gel column using the same solvent mixture as eluent. A
major brown-green fraction was collected and after evapo-
ration gave Co3(l3-CCBCSiMe3)(l-dppm)(CO)7 (4)
(75 mg, 86%) as dark green crystals (hexane). Anal. Calc.
for C38H31Co3O7P2Si (MW = 866): C, 52.68; H, 3.61.
Found: C, 52.64; H, 3.62. IR (CH2Cl2, cmꢀ1): m(CBC)
1
2138vw; m(CO) 2065s, 2048s, 2010vs, 1990 (sh). H NMR:
d 0.32 (s, 9H, SiMe3), 3.49, 4.54 (2 · m, 2 · 1H, CH2),
7.13–7.58 (m, 20H, Ph). 13C NMR: d 0.10 (s, SiMe3),
39.52 [t, J(CP) 25.4 Hz, dppm], 116.70, 126.19 (2 · s,
carbon chain), 128.22–137.28 (m, Ph), 202.13, 210.08,
225.14 [s (br), CO]. 31P NMR: d 33.3 [s (br), dppm]. ES-
MS (positive ion, MeOH + NaOMe, m/z): 889,
[M+Na]+; (negative ion, MeOH + NaOMe, m/z), 865,
[MꢀH]ꢀ.
4.6.1.6. R = C6H4I (7). A solution containing Co3{l3-
CCBCAu(PPh3)}(l-dppm)(CO)7 (50 mg, 0.04 mmol),
1,4-I2C6H4 (6.4 mg, 0.02 mmol), Pd(PPh3)4 (5 mg,
0.004 mmol) and CuI (1 mg, 0.006 mmol) in thf (3 ml)
was stirred at r.t. for 6 h. After removal of solvent, the
residue was extracted with CH2Cl2 and separated by pre-
parative t.l.c. (acetone–hexane 3/7) into two fractions.
Band 1 (Rf 0.50, green) contained Co3(l3-CCBCC6H4I-
4)(l-dppm)(CO)7 (7) (12.2 mg, 61%), obtained as very
dark green crystals (CH2Cl2/MeOH). Anal. Calc. for
C41H26Co3IO7P2 (MW = 996): C, 49.40; H, 2.61. Found:
C, 49.65; H, 2.31%. IR (CH2Cl2, cmꢀ1): m(CBC) 2117vw;
Method B: A solution of Co3(l3-CBr)(l-dppm)(CO)7
(200 mg, 0.24 mmol) and HCBCSiMe3 (48 mg, 0.5 mmol)
in thf (10 ml) was treated with CuI (2 mg, 0.012 mmol)
and Pd(PPh3)4 (14 mg, 0.012 mmol), followed by addition
of dbu (several drops). After stirring at r.t. for 2 h, work-
up as above gave Co3(l3-CCBCSiMe3)(l-dppm)(CO)7 (4)
(157 mg, 75%). A minor product formed on some occa-
sions was identified as {Co3(l-dppm)(CO)7}2(l3:l3-C6)
[10a].
1
m(CO) 2060s, 2010vs, 1980 (sh), 1967 (sh), 1949 (sh). H
4.6.1.4. R = Fc (5). Thf (10 ml) was added to a solid
mixture of Au(CBCFc)(PPh3) (100 mg, 0.15 mmol),
NMR: d 3.40, 4.37 (2 · s, 2 · 1H, dppm), 7.05–7.69 (m,
24H, Ph + C6H4). 31P NMR: d 34.3 [s (br), dppm]. ES-
MS (positive ion, MeOH + NaOMe, m/z): 1019,
[M+Na]+; (negative ion, MeOH, m/z): 995, [MꢀH]ꢀ;
967, [MꢀHꢀCO]ꢀ. The second orange-brown band (Rf
0.45) contained 1,4-{(OC)7(l-dppm)Co3(l3-CCBC)}2
C6H4 (8) (3.6 mg, 11%), identified by comparison with
a sample prepared as described below.
Co3(l3-CBr)(l-dppm)(CO)7
(127 mg,
0.15 mmol),
Pd(PPh3)4 (17 mg, 0.015 mmol) and CuI (3 mg,
0.015 mmol) and the reaction was stirred at r.t. for 1 h.,
after which spot t.l.c. showed the absence of starting
materials. After evaporation of thf, the residue was
extracted with CH2Cl2 and purified by preparative t.l.c.
(acetone–hexane 1/4). One brown band developed (Rf
0.43) and contained Co3(l3-CCBCFc)(l-dppm)(CO)7 (5)
(134 mg, 91%) as very dark red crystals (CH2Cl2/MeOH).
X-ray quality crystals were obtained as the mono-CHCl3
solvate from CHCl3/hexane. Anal. Calc. for C45H31Co3-
FeO7P2 (MW = 978): C, 55.22; H, 3.17. Found: C,
55.19; H, 3.20%. IR (CH2Cl2, cmꢀ1): m(CBC) 2123vw;
4.6.1.7. R = C6H4CBCPh (9). A mixture of Au(CBC-
C6H4CBCPh-4)(PPh3) (90 mg, 0.14 mmol), Co3(l3-CBr)-
(l-dppm)(CO)7 (116 mg, 0.14 mmol), Pd(PPh3)4 (7.2 mg,
0.006 mmol) and CuI (1.3 mg, 0.006 mmol) in thf (10 ml)
was stirred at r.t. for 2.5 h. After removal of solvent, the res-
idue was extracted with CH2Cl2 and separated by prepara-
tive t.l.c. (hexane–acetone 10/1). The major brown band (Rf
0.56) contained Co3(l3-CCBCC6H4CBCPh)(l-dppm)-
(CO)7 (9) (51 mg, 39%) which was isolated as dark brown
crystals (CH2Cl2/MeOH). Anal. Calc. for C49H31Co3O7P2
(MW = 970): C, 60.62; H, 3.19. Found: C, 60.61; H,
3.17%. IR (CH2Cl2, cmꢀ1): m(CBC) 2115vw, 2100vw;
m(CO) 2059s, 2011vs, 1993 (sh), 1967 (sh). 1H NMR: d
3.40, 4.43 (2 · s, 2 · 1H, dppm), 7.18–7.52 (m, 29H,
Ph + C6H4). 13C NMR: d 41.27 [t, J(CP) 22.5 Hz, PCH2],
89.70, 91.10 (2 · s, CBCC6H4CBC), 110.37 (s, C3), 114.19
1
m(CO) 2057s, 2007vs, 1988 (sh), 1965 (sh), 1948 (sh). H
NMR: d 3.40, 4.41 (2 · s, 2 · 1H, dppm), 4.20 (s, 5H,
Cp), 4.33, 4.48 (2 · m, 2 · 2H, C5H4), 7.12–7.59 (m,
20H, Ph). 13C NMR: d 40.49 [t, J(CP) 21.4 Hz, dppm],
69.84 (s, Cp), 69.14, 70.45 (2 · s, Ca, Cb, C5H4), 67.99
(Cipso, C5H4), 107.95, 111.77 (2 · s, chain carbons),
128.24–145.06 (m, Ph), 202.44, 212.58, 226.21 [s (br),
CO]. 31P NMR: d 33.7 (s, dppm). ES-MS (positive ion
mode, MeOH, m/z): 978, M+; 950, [MꢀCO]+; (negative
ion, MeOH, m/z): 977, [MꢀH]ꢀ.

4704
A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
(s, C2), 121.80-135.96 (m, Ph), 202.15, 210.05, 221.73 (3 · s,
br, CO). 31P NMR: d 34.3 (s, dppm). ES-MS (positive ion,
MeOH + NaOMe, m/z): 993, [M+Na]+; (negative ion,
MeOH + NaOMe, m/z): 969, [MꢀH]ꢀ.
at r.t., work-up as above afforded a green-brown
band (Rf 0.47) which contained 1,3-{(OC)7(l-
dppm)Co3(l3-CCBC)}2C6H3Br-5 (11) (10.8 mg),
obtained as brown-red crystals (CH2Cl2/MeOH).
Crystals of a CH2Cl2-solvate for the X-ray study were
obtained by recrystallisation from the same solvent
mixture. Anal. Calc. for C76H47BrCo6O14P4 (MW =
1742): C, 52.38; H, 2.69. Found: C, 52.34; H,
2.61%. IR (CH2Cl2, cmꢀ1): m(CBC) 2114w; m(CO)
2057s, 2009vs, 1988 (sh), 1970 (sh), 1951 (sh). 1H
NMR: d 3.40, 4.41 (2 · m, 2 · 2H, CH2), 6.95–7.51
(m, 43H, Ph + C6H3). 31P NMR: d 35.2 [s (br),
dppm]. ES MS (positive ion, MeOH + NaOMe,
m/z): 1765, [M+Na]+; (negative ion, MeOH +
NaOMe, m/z): 1741, [MꢀH]ꢀ.
4.7. Preparation of 1,4-{(OC)7(l-dppm)Co3}2{(l3-
CCBC)}2C6H4 (8)
A
mixture of 1,4-{Au(PPh3)(CBC)}2C6H4 (30 mg,
0.03 mmol), Co3(l3-CBr)(l-dppm)(CO)7 (98 mg,
0.06 mmol), Pd(PPh3)4 (15 mg, 0.013 mmol) and CuI
(5 mg, 0.026 mmol) was stirred in thf (20 ml) at r.t. for
1 h. The solvent was then removed and the resulting dark
purple residue purified by preparative t.l.c. eluting with
acetone/hexane (2:3) to obtain 1,4-{(OC)7(l-dppm)Co3}2-
{(l3-CCBC)}2C6H4 (8) as an orange band (Rf 0.68)
(20.3 mg, 41%). Anal. Calc. for C76H48P4Co6O14 (MW =
1662): C, 54.87; H, 2.89. Found: C, 54.92; H, 2.75%. IR
(CH2Cl2, cmꢀ1): m(CBC) 2114w, m(CO) 2059s, 2010vs
1993sh(m), 1969sh(w). 1H NMR: d 3.42, 4.44 (2 · m,
2 · 2H, CH2), 7.18–7.50 (m, 44H, Ph + C6H4). 31P NMR
(CDCl3): d 37.0 (s, br, 4P, dppm). ES MS (positive ion,
MeOH + NaOMe, m/z): 1685 [M+Na]+; (negative ion,
MeOH, m/z): 1661, [MꢀH]ꢀ.
4.9. 1,10-{(OC)7(l-dppm)Co3(l3-CCBC)}2Fc0 (12)
A
solution containing 1,10-Fc0{CBCAu[P(tol)3]}2
(26 mg, 0.02 mmol), Co3(l3-CBr)(l-dppm)(CO)7 (36 mg,
0.04 mmol), Pd(PPh3)4 (1 mg, 0.001 mmol) and CuI
(1 mg, 0.005 mmol) in thf (5 ml) was stirred at r.t. for
2 h. After removal of solvent, the residue was extracted
with CH2Cl2 and purified by preparative t.l.c. (acetone–
hexane 3/7) to give one major band (Rf 0.34), from which
1,10-{(OC)7(l-dppm)Co3(l3-CCBC)}2Fc0 (12) (35.7 mg,
96%) was isolated as very dark red crystals (CH2Cl2/
MeOH). Anal. Calc. for C80H52Co6FeO14P4 (MW =
1770): C, 54.23; H, 2.94. Found: C, 54.26; H, 2.96%. IR
(CH2Cl2, cmꢀ1): m(CBC) 2122vw; m(CO) 2057s, 2008vs,
1989 (sh), 1977 (sh), 1964 (sh). 1H NMR: d 3.43, 4.44
(2 · s, 2 · 1H, dppm), 4.40, 4.53 (2 · m, 2 · 4H, C5H4),
7.11–7.52 (m, 40H, Ph). 31P NMR: d 33.7 [s (br), dppm].
ES-MS (positive ion, MeOH + NaOMe, m/z): 1793,
[M+Na]+; (negative ion, MeOH, m/z): 1769, [MꢀH]ꢀ.
4.8. Reaction of 1,3,5-{(Ph3P)AuCBC}3C6H3 with Co3(l3-
CBr)(l-dppm)(CO)7
(a) A solution of 1,3,5-{(Ph3P)AuCBC}3C6H3 (59.7 mg,
0.039 mmol) and Co3(l3-CBr)(l-dppm)(CO)7 (100
mg, 0.118 mmol) in thf (10 ml) was treated with
Pd(PPh3)4 (4.5 mg, 0.0035 mmol) and CuI (1 mg,
0.005 mmol) and the mixture was stirred at r.t. for
4 h. After removal of solvent under vacuum, a
CH2Cl2 extract of the residue was purified by pre-
parative t.l.c. (acetone–hexane, 3/7). The major
brown band (Rf 0.40) contained 1,3,5-{(OC)7(l-
dppm)Co3(l3-CCBC)}3C6H3 (10) (48.8 mg, 50%),
obtained as dark red crystals (CHCl3/MeOH).
CHCl3-solvated crystals were obtained for the X-
4.10. Co3{l3-C(CBC)3R}(l-dppm)(CO)7
4.10.1. R = SiMe3 (13)
A mixture of Co3{(l3-CCBCCB)CAu(PPh3)}(l-dppm)
(CO)7 (280 mg, 0.219 mmol), ICBCSiMe3 (85 mg, 0.379
mmol), Pd(PPh3)4 (13 mg, 0.01 mmol) and CuI (2 mg,
0.01 mmol) in thf (10 ml) was stirred at r.t. for 2 h. After
removal of solvent, preparative t.l.c. (acetone–hexane 1/2)
of a CH2Cl2 extract of the residue developed two bands.
Band 1 (Rf 0.55, brown) contained Co3{l3-C(CBC)3-
SiMe3}(l-dppm)(CO)7 (13) (108 mg, 54%), obtained a
brown-black crystals from CH2Cl2/MeOH. Anal. Calc.
for C42H31Co3O7P2Si (MW = 914): C, 55.16; H, 3.42.
Found: C, 55.20; H, 3.48%. IR (CH2Cl2, cmꢀ1): m(CBC)
ray study. Anal. Calc. for
C111H69Co9O21P6
(MW = 2454): C, 54.28; H, 2.83. Found: C, 54.80;
H, 2.83%. IR (CH2Cl2, cmꢀ1): m(CBC) 2115w;
m(CO) 2059s, 2010vs, 1990 (sh), 1969 (sh), 1953 (sh).
1H NMR: d 3.46, 4.43 (2 · m, 2 · 3H, CH2), 7.17–
7.58 (m, 63H, Ph + C6H3). 13C NMR: d 40.81 [s
(br), CH2], 108.92, 112.76 (2 · s, 2 · C of C3 chain),
126.54–132.17 (m, Ph + C6H3), 202.24 [s (br), CO].
31P NMR: d 35.0 [s (br), dppm]. ES MS (positive
ion, MeOH, m/z): 2454, M+; (MeOH + NaOMe,
m/z): 2477, [M+Na]+.
1
2134vw; m(CO) 2062s, 2018vs, 1974 (sh). H NMR: d 0.26
(b) From a sample of 1,3,5-{(Ph3P)AuCBC}3C6H3 con-
taining a significant amount of 1,3-{(Ph3P)AuC
BC}2C6H3Br-5, a similar reaction with Co3(l3-
CBr)(l-dppm)(CO)7 (33 mg, 0.039 mmol) was carried
out with the addition of a few drops of dbu. After 2 h
(s, 9H, SiMe3), 3.41, 4.24 (2 · s, 2 · 1H, dppm), 7.20–7.41
(m, 20H, Ph). 31P NMR: d 34.6 (s, dppm). ES-MS (positive
ion, MeOH + NaOMe, m/z): 937, [M+Na]+; 915,
[M+H]+; 865, [M+H+NaꢀSiMe3]+; (negative ion,
MeOH + NaOMe, m/z): 913, [MꢀH]ꢀ; 841, [MꢀSiMe3]ꢀ;

A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
4705
Table 2
Crystal data and refinement details
Complex
2
3 Æ CH2Cl2
4
5 Æ CHCl3
Formula
C39H31Co3O7P2
850.42
Triclinic
C41H27Co3O7P2 Æ CH2Cl2
955.34
Monoclinic
P21/n
15.819(1)
11.869(1)
C38H31Co3O7P2Si
866.49
Triclinic
C45H31Co3FeO7P2 Æ CHCl3
1097.71
Triclinic
Molecular weight
Crystal system
Space group
ꢀ
ꢀ
ꢀ
P1
P1
P1
˚
a (A)
11.551(2)
11.951(2)
14.206(3)
86.870(5)
77.758(5)
87.216(5)
1912
11.497(2)
11.847(2)
14.230(3)
86.192(4)
77.441(4)
86.772(4)
1886
13.388(2)
15.437(2)
23.798(4)
103.256(3)
91.655(3)
111.921(3)
4405
˚
b (A)
˚
c (A)
22.280(2)
a (ꢁ)
b (ꢁ)
c (ꢁ)
103.505(2)
3
˚
V (A )
4067
1.560
qc (g cmꢀ3
)
1.477
1.526
1.655
Z
2
4
2
4
2hmax (ꢁ)
75
1.42
0.87
70
1.47
0.88
65
1.47
0.85
50
1.74
0.69
l(Mo Ka) (mmꢀ1
Tmin/max
)
Crystal dimensions (mm)
Ntot
0.46 · 0.25 · 0.20
36883
0.38 · 0.32 · 0.25
72089
0.43 · 0.35 · 0.28
38998
0.25 · 0.20 · 0.10
60143
N (Rint
N0
)
18952 (0.028)
14566
17984 (0.053)
11543
13305 (0.034)
10511
14912 (0.085)
11005
R
0.037
0.044
0.038
0.065
Rw (nw)
0.048 (8)
0.049 (6)
0.045 (5)
0.132 (40)
6
7
9
10 Æ 2CHCl3
Formula
C53H37AuCo3O7P3
1252.56
Triclinic
C41H26Co3IO7P2
996.30
Triclinic
C49H31Co3O7P2
970.53
Orthorhombic
Pbca
C111H69Co9O21P6 Æ 2CHCl3
2693.75
Triclinic
Molecular weight
Crystal system
Space group
ꢀ
ꢀ
ꢀ
P1
P1
P1
˚
a (A)
13.687(2)
13.764(2)
14.039(2)
89.615(4)
78.234(4)
69.498(4)
2419
10.550(1)
11.467(1)
18.061(2)
73.721(2)
81.711(2)
66.440(2)
1921
12.214(2)
22.689(3)
30.421(4)
17.615(5)
18.507(5)
19.930(6)
68.971(5)
74.113(5)
71.475(5)
5656
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
8431
1.529
qc (g cmꢀ3
)
1.719
1.722
1.582
Z
2
2
8
2
2hmax (ꢁ)
66.5
4.2
0.68
65
2.22
0.61
52
1.30
0.84
45
1.58
0.79
l(Mo Ka) (mmꢀ1
Tmin/max
)
Crystal dimensions (mm)
Ntot
0.28 · 0.23 · 0.16
39993
0.52 · 0.20 · 0.15
30132
0.85 · 0.05 · 0.04
69472
0.33 · 0.28 · 0.05
41488
N (Rint
N0
)
18377 (0.053)
13474
13651 (0.043)
9372
8090 (0.074)
6420
14868 (0.12)
8601
R
0.041
0.046
0.047
0.16
Rw (nw)
0.044 (4)
0.051 (6)
0.059 (15)
0.26 (328)
11 Æ CH2Cl2
12
13
16
Formula
C
76H47Co6O14P4 Æ CH2Cl2
C80H52Co6FeO14P4
1770.62
Monoclinic
P21/c
11.294(1)
19.911(2)
C42H31Co3O7P2Si
914.54
Monoclinic
P21/n
18.271(2)
12.644(1)
19.171(2)
C45H27Co3O7P2
918.45
Monoclinic
P21/c
10.044(1)
25.238(2)
16.303(2)
Molecular weight
Crystal system
Space group
1826.53
Monoclinic
P21/c
17.054(3)
20.202(3)
21.897(3)
˚
a (A)
˚
b (A)
˚
c (A)
17.047(2)
a (ꢁ)
b (ꢁ)
c (ꢁ)
V (A )
qc (g cmꢀ3
100.459(2)
102.174(2)
114.498(2)
94.785(2)
3
˚
7419
1.635
4
3747
1.581
2
4030
1.507
4
4118
1.481
4
)
Z
2hmax (ꢁ)
58
2.07
58
1.63
58
1.38
65
1.32
l(Mo Ka) (mmꢀ1
)
(continued on next page)

4706
A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
Table 2 (continued)
11 Æ CH2Cl2
12
13
16
Tmin/max
Crystal dimensions (mm)
Ntot
0.79
0.88
0.77
0.86
0.28 · 0.15 · 0.08
71451
0.32 · 0.15 · 0.13
21820
0.56 · 0.41 · 0.12
57543
0.20 · 0.12 · 0.10
72405
N (Rint
N0
)
18439 (0.045)
13097
9750 (0.031)
7363
10606 (0.075)
7553
17960 (0.060)
10430
R
0.045
0.044
0.048
0.046
Rw (nw)
0.053 (1.5)
0.054 (10)
0.098 (3000)
0.062 (20)
814, [M+HꢀCOꢀSiMe3]ꢀ. Band 2 (Rf 0.38, red-brown)
contained {Co3(l-dppm)(CO)7}2(l3:l3-C10), identified by
comparison with an authentic sample [10a].
35H, Ph). 13C NMR: d 42.63 (m, CH2), 57.49, 82.83,
88.79, 95.20, 98.81 (5 · s, carbon chain), 128.38–131.86
(m, Ph), 134.20–134.52 (m, Ph), 201.52 (br, CO). 31P
NMR: d 34.7 [s (br), dppm]. ES-MS (positive ion,
MeOH + NaOMe, m/z): 1323, [M+Na]+.
4.10.2. R = Fc (14)
A mixture of Co3{l3-CCBCCBCAu(PPh3)}(l-dppm)-
(CO)7} (60 mg, 0.05 mmol), FcCBCI (15.3 mg, 0.05
mmol), Pd(PPh3)4 (3 mg, 0.0025 mmol) and CuI (1 mg,
0.005 mmol) in thf (7 ml) was stirred at r.t. for 30 min.
Evaporation and purification of the residue by preparative
t.l.c. (acetone/hexane 1/4) gave three bands. The fastest
moving (Rf 0.93) contained FcCBCCBCFc (2 mg, 5%),
identified by comparison with an authentic sample [26].
The major product was contained in the second brown-
orange band (Rf 0.26), which gave Co3{(l3-CCBC)3-
Fc}(l-dppm)(CO)7 (14) (40.8 mg, 87.4%) as very thin red
plates (CH2Cl2/hexane). Anal. Calc. for C49H31Co3FeO7P2
(MW = 1026): C, 57.31; H, 3.02. Found: C, 56.74; H,
2.57%. IR (CH2Cl2, cmꢀ1): m(CBC) 2168w, 2100vw;
4.10.4. R = Ph (16)
A solution containing Co3{l3-CCBCCBCAu(PPh3)}-
(l-dppm)(CO)7} (50 mg, 0.04 mmol) and Pd(PPh3)4
(3 mg, 0.0025 mmol) in thf (5 ml) was added to a mixture
of iodine (10 mg, 0.04 mmol) and CuI (1 mg, 0.005 mmol)
in thf (5 ml) at ꢀ78 ꢁC, and the mixture was stirred for
1 h. After this time, a solution of Au(CBCPh)(PPh3)
(20 mg, 0.04 mmol) in thf (5 ml) was added dropwise and
the mixture was stirred for a further 1 h at ꢀ78 ꢁC. After
allowing to warm to r.t., the filtered soluton was evapo-
rated and the residue was extracted into CH2Cl2 and puri-
fied by preparative t.l.c. (acetone–hexane 3/7). The brown
band (Rf 0.76) contained Co3{(l3-CCBC)3Ph}(l-dppm)-
(CO)7 (16) (21 mg, 60%), obtained as black needles
(CH2Cl2/MeOH). Anal. Calc. for C45H27Co3O7P2
(MW = 918): C, 58.82; H, 2.94. Found: C, 58.98; H,
2.87%. IR (CH2Cl2, cmꢀ1): m(CBC) 2190w, 2171vw;
m(CO) 2063s, 2013vs, 1973 (sh), 1958 (sh) cmꢀ1 1H
.
NMR: d 3.40, 4.25 (2 · m, 2 · 1H, CH2), 4.28 (s, 5H,
Cp), 4.30, 4.56 (2 · m, 2 · 2H, C5H4), 7.15–7.69 (m, 20H,
Ph). 13C NMR: d 42.75 [t, J(CP) 18.3, CH2P], 70.35 (s,
Cp), 69.76, 72.35 (2 · m, C5H4), 63.38, 65.66, 72.73,
80.95, 85.99, 97.13, 99.03 (Cipso of C5H4 + six C of C7
chain), 201.43, 209.79, 212.4 (3 · s, CO). 31P NMR: d
33.8 (s, dppm). ES-MS (positive ion, MeOH, m/z): 1027,
[M+H]+; 1026, [M]+; 998, [MꢀCO]+; (positive ion,
MeOH + NaOMe, m/z): 1049, [M+Na]+; (negative ion,
MeOH + NaOMe, m/z): 1025, [MꢀH]ꢀ. The third band
(Rf 0.15, brown-orange) contained {Co3(l-dppm)(CO)7}2-
(l3:l3-C10) (0.6 mg, 1%), identified by comparison with
an authentic sample [10a].
m(CO) 2065s, 2040m, 2014m, 1973 (sh), 1955 (sh) cmꢀ1
.
1H NMR: d 3.30, 4.15 (2 · m, 2 · 1H, dppm), 7.09–7.47
(m, 25H, Ph). 31P NMR: d 34.6 (s, dppm). ES-MS (positive
ion, MeOH + NaOMe, m/z): 941, [M+Na]+; (negative ion,
MeOH, m/z): 917, [MꢀH]ꢀ; 889, [MꢀHꢀCO]ꢀ.
4.11. Structure determinations
Full spheres of diffraction data were measured at ca.
153 K using a Bruker AXS CCD area-detector instrument.
Ntot reflections were merged to N unique (Rint cited) after
‘‘empirical’’/multiscan absorption correction (proprietary
software), N0 with F > 4r(F) being used in the full matrix
least squares refinements. All data were measured using
monochromatic Mo Ka radiation, k = 0.71073 A. Aniso-
tropic displacement parameter forms were refined for the
non-hydrogen atoms, (x,y,z,Uiso H being included, con-
strained at estimates. Conventional residuals R, Rw on |F|
are quoted [weights: (r2(F) + 0.000nwF2)ꢀ1]. Neutral atom
complex scattering factors were used; computation used
the XTAL 3.7 program system [39]. Pertinent results are given
in the figures (which show non-hydrogen atoms with 50%
probability amplitude displacement ellipsoids and hydrogen
4.10.3. R = Au(PPh3) (15)
NaOMe [from 10 mg Na in MeOH (10 ml)] was added
to a solution of Co3{l3-C(CBC)3SiMe3}(l-dppm)(CO)7
(84 mg, 0.092 mmol) in thf/MeOH (1/1, 10 ml), and after
stirring for 10 min at r.t., AuCl(PPh3) (46 mg, 0.093 mmol)
was added. A brown precipitate separated and after stirring
at r.t. for 1 h, the precipitate was collected and washed with
MeOH (2 · 2 ml) affording Co3{l3-C(CBC)3Au(PPh3)}(l-
dppm)(CO)7 (15) (90 mg, 75%) as a brown powder. Anal.
Calc. for C57H37AuCo3O7P3 (MW = 1300): C, 52.64; H,
2.87. Found: C, 52.59; H, 2.83%. IR (CH2Cl2, cmꢀ1):
m(CBC) 2117vw; m(CO) 2060s, 2012vs, 1974 (sh). 1H
NMR: d 3.40, 4.34 (2 · s, 2 · 1H, dppm), 7.18–7.56 (m,
˚
)
˚
atoms with arbitrary radii of 0.1 A) and in Tables 1 and 2.

A.B. Antonova et al. / Journal of Organometallic Chemistry 691 (2006) 4694–4707
4707
[10] (a) M.I. Bruce, M.E. Smith, N.N. Zaitseva, B.W. Skelton, A.H.
White, J. Organomet. Chem. 670 (2003) 170;
Variata. 4. (x,y,z,Uiso H were refined throughout; it is
isomorphous with 2 and was refined in the same cell and
coordinate setting.
)
(b) M.I. Bruce, B.W. Skelton, A.H. White, N.N. Zaitseva, J.
Organomet. Chem. 683 (2003) 398.
5. The iron atoms of both molecules were modelled as
disordered over pairs of sites, occupancies refining in con-
cert to 0.888(3) and complement. Feꢁ ꢁ ꢁFe are 0.88(1) and
[11] R. Markby, I. Wender, R.A. Friedel, F.A. Cotton, H.W. Sternberg,
J. Am. Chem. Soc. 80 (1958) 6529.
[12] G. Palyi, F. Piacenti, L. Marko, Inorg. Chim. Acta Rev. 4 (1970) 109.
[13] B.R. Penfold, B.H. Robinson, Acc. Chem. Res. 6 (1973) 73.
[14] D. Seyferth, Adv. Organomet. Chem. 14 (1976) 97.
[15] G. Schmid, Angew. Chem. 90 (1978) 417; Angew. Chem., Int. Ed.
Engl. 17 (1978) 392.
[16] R.D.W. Kemmitt, in: G. Wilkinson, F.G.A. Stone, E.W. Abel (Eds.),
Comprehensive Organometallic Chemistry, vol. 5, Pergamon, Oxford,
1982, p. 162 (Chapter 34.3.9).
˚
0.86(1) A; minor components of the associated Cp ligands
were not located.
10. Weak and limited data resulted in a determination of
inferior precision. Refinement on F2.
11. The dichloromethane of solvation was modelled as
disordered over two sets of sites, occupancies 0.694(5)
and complement.
[17] C.E. Barnes, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 8, Pergamon,
Oxford, 1995, p. 423 (Chapter 4.3.1.2).
13. Refinement on F2.
[18] (a) R.J. Dellaca, B.R. Penfold, B.H. Robinson, W.T. Robinson, J.L.
Spencer, Inorg. Chem. 9 (1970) 2204;
5. Supplementary material
(b) R.J. Dellaca, B.R. Penfold, Inorg. Chem. 10 (1971) 1269.
[19] G.H. Worth, B.R. Robinson, J. Simpson, Organometallics 11 (1992)
501.
[20] D. Seyferth, R.J. Spohn, M.R. Churchill, K. Gold, F.J. Scholer,
Organomet. Chem. 23 (1970) 237.
[21] 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, N.N. Zaitseva, Chem. Commun. (2004)
960.
[22] (a) A.J. Downard, B.H. Robinson, J. Simpson, Organometallics 5
(1986) 1122;
Full details of the structure determinations (except
structure factors) have been deposited with the Cambridge
Crystallographic Data Centre as CCDC 284347–284358.
Copies of this information may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (fax: + 44 1223 336 033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
Acknowledgement
(b) A.J. Downard, B.H. Robinson, J. Simpson, Organometallics 5
(1986) 1132;
(c) A.J. Downard, B.H. Robinson, J. Simpson, Organometallics 5
(1986) 1140.
[23] S. Aime, L. Milone, M. Valle, Inorg. Chim. Acta 18 (1976) 9.
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[25] J. Hlavaty, L. Kavan, M. Sticha, J. Chem. Soc., Perkin Trans. 1
(2002) 705.
We thank the ARC for support of this work.
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