Lithiation of diynyl-ruthenium complexes: Routes to novel metallated functional diynes

Article abstract of DOI:10.1016/j.jorganchem.2011.07.021

Conditions for the efficient lithiation of the diynyl group in complexes Ru(CCCCH)(PP)Cp′ [(PP)Cp′ = (dppe)Cp (*) 1, (PPh ₃)₂Cp 2 have been investigated. Addition of two equiv. LiBu to the diynyl complexes in thf solution at -78°C effects rapid conversion to putative Ru(CCCCLi)(PP)Cp′. Assays using subsequent reactions with either SiClMe₃ or AuCl(PPh₃) indicate that up to 80% conversion can be achieved. Reactions of the lithiated species with organic electrophiles [MeI, MeC(O)Cl, PhC(O)Cl, ClC(O)OMe, PhCHO, Ph ₂CO and metal-containing substrates [MClPh₃ (M = Ge, Sn), trans-RhCl(CO)(PPh₃)₂, cis-PtCl₂(PPh ₃)₂, CuCl(PPh₃), (AuCl)₂(μ-dppm) proceed to give functionalised diynyl complexes or bimetallic derivatives which are accessible only with difficulty or not at all from the parent diynes. Single-crystal X-ray diffraction molecular structures of Ru(CCCCR)(dppe)Cp (*) (R = Me, GePh₃) are reported: there is significantly greater delocalisation along the Ru-C₄-R chain in the GePh ₃ derivative.

Full text of DOI:10.1016/j.jorganchem.2011.07.021

Journal of Organometallic Chemistry 696 (2011) 3473e3482
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Lithiation of diynyleruthenium complexes: Routes to novel metallated
functional diynes
,
a
b
Michael I. Bruce a , Nancy Scoleri , Brian W. Skelton
*
a School of Chemistry and Physics, University of Adelaide, Adelaide 5005, Australia
b Centre for Microscopy, Characterisation and Analysis, University of Western Australia, Crawley 6009, Australia
a r t i c l e i n f o
a b s t r a c t
Conditions for the efficient lithiation of the diynyl group in complexes Ru(C^CC^CH)(PP)Cp0 [(PP)
Cp0 ¼ (dppe)Cp* 1, (PPh3)2Cp 2] have been investigated. Addition of two equiv. LiBu to the diynyl
complexes in thf solution at ꢀ78ꢁC effects rapid conversion to putative Ru(C^CC^CLi)(PP)Cp0. Assays
using subsequent reactions with either SiClMe3 or AuCl(PPh3) indicate that up to 80% conversion can be
achieved. Reactions of the lithiated species with organic electrophiles [MeI, MeC(O)Cl, PhC(O)Cl, ClC(O)
OMe, PhCHO, Ph2CO] and metal-containing substrates [MClPh3 (M ¼ Ge, Sn), trans-RhCl(CO)(PPh3)2, cis-
Article history:
Received 29 April 2011
Received in revised form
15 July 2011
Accepted 15 July 2011
Keywords:
Diynyl
Ruthenium
Lithiation
X-ray structure
PtCl2(PPh3)2, CuCl(PPh3), (AuCl)2(m-dppm)] proceed to give functionalised diynyl complexes or bimetallic
derivatives which are accessible only with difficulty or not at all from the parent diynes. Single-crystal X-
ray diffraction molecular structures of Ru(C^CC^CR)(dppe)Cp* (R ¼ Me, GePh3) are reported: there is
significantly greater delocalisation along the RueC4eR chain in the GePh3 derivative.
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
AuC(NMe2)]C]C]M(CO)5 occurs upon standing in solution
[3]. Extension of the carbon chain was achieved by reaction of
Although lithiated alkynes and poly-ynes have proved to be useful
reagents for the syntheses of other compounds through their reac-
tions with electrophiles [1], there have been relatively few accounts
of the lithiation of metalla-alkynes, poly-ynes and other carbon-rich
complexes. These intermediates would provide access to a wide
variety of functionalised complexes which are accessible with diffi-
culty or not at all from the parent alkynes or poly-ynes. Examples of
all-carbon ligands which have been successfully metallated and
subsequently derivatised include C, C2 and C4 species include:
the ethynylcarbene with LiBu/I2 to give IC^CC(NMe2)]
M(CO)5, followed by Cu(I)-catalysed coupling with
IC^CeC^CSiMe to give (OC)5W]C(NMe2)(C^C)3SiMe3,
desilylation and reaction with LiBu/HgCl2 to give Hg
{(C^C)3C(NMe2)]W(CO)5}2.
(b) Vinylidenes. Deprotonation of [Ru(]C]CH2)P2Cp*]þ (P ¼ PMe3,
PPh3) with KOBut gives Ru(C^CH)P2Cp* which with LiBu or
LiBut is further deprotonated to LiC^CRuP2Cp*. The lithio
derivative reacts with ECl (E ¼ SiMe3, GeMe3, SnBu3, PPh2) to
give Ru(C^CE)P2Cp* [4]. Double or triple deprotonation of
[Ru(]C]CH2)(PPh3)2Cp]þ occurs with more than one equiv.
LiBut, as shown by subsequent reactions with MeI or SiClMe3 [5].
Metallation of Ru(C^CH)(PPh3)2Cp with LiBu, or treatment of
[Ru(]C]CH2)(dppe)Cp*]þ with two equivalents of LiBu, fol-
lowed by addition of PhOCN, gave Ru(C^CCN)(PPh3)2Cp and
Ru(C^CCN)(dppe)Cp*, respectively [6].
(a) Carbenes.
Fischer-type
ethynyl-carbene
complexes
HC^CC(NMe2)]M(CO)5 (M ¼ Cr, W) have been metallated
with LiBu, subsequent reactions with a range of Main Group
halides (BBr3, SiCl4, GeCl4, SnCl4, PCl3) affording E{C^CC
(NMe2)]W(CO)5}x (E ¼ B, P, x ¼ 3, E ¼ Si, Ge, S, x ¼ 4). and LnM
{C^CC(NMe2)]M(CO)5} [LnM ¼ trans-FeCl(dmpe)2, trans-
PdCl(PEt3)2, trans-PdCl(C^CH)(PEt3)2, Au(PPh3), to give mono-
substituted products; TiCl2Cp2, trans-FeCl2(dmpe)2, MCl2
(PEt3)2 (M ¼ Ni, Pd, Pt), HgCl2, to give disubstituted complexes]
[2,3]. Isomerisation of the Au(PPh3) derivative to (Ph3P)
Related reactions were reported earlier, when addition of LiMe
to Mn(h-HC2CO2Me)(CO)2Cp followed by quenching with electro-
philes (MeOTf) afforded Mn(]C]CMe2)(CO)2Cp in a reaction
thought to proceed via loss of Me2CO from an intermediate Li2[Mn
{]C]CC(O)Me2}(CO)2Cp] to give Li2[Mn(]C]C)(CO)2Cp] [7].
* Corresponding author. Fax: þ 61 8 8303 4358.
E-mail addresses: michael.bruce@adelaide.edu.au, mbruce@chemistry.adelaide.
edu.au (M.I. Bruce).
(c) Carbynes. Lithiocarbynes LiC^M(CO)2Tp* [M ¼ Mo, W;
Tp* ¼ HB(Me2-pz)3] have been obtained directly from
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.07.021

3474
M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
M(^CBr)(CO)2Tp* and LiBu [8], or from HC^W(CO)2Tp* with
(f) Alkynes. Treatment of Co2(
reported to give dark green-black Co2(
as indicated by formation of
m-HC^CSiMe3)(CO)6 with LiNR2 is
LiBu, LiBut or solid LiNMe2 (LDA) [9]. Further reactions with
electrophiles I2, MeI, SiMe3(OTf), Ph2C]O, PhCHO and PhCOBr
[9] or with NBS, H2O, MeI, SiMe3Cl, Ph2S2, Ph2Se2, Sen, Ten and
FeCl(CO)2Cp [8] were reported. More recently, detailed insights
into reactions of the supposed metallated carbynes suggest
that not only competitive reactions between side-products,
such as BuBr (which can act as proton donor or nucleophile),
but oxidation [single-electron transfer to give a radical carbide
complex Mo(^Cꢂ)(CO)2Tp*] may occur [10].
m-LiC^CSiMe3)(CO)6,
{Co2(CO)6}n(Me3
-
SiC^CC^CSiMe3) (n ¼ 1, 2) with electrophiles as a result of
reactions involving single electron transfer. Similarly,
{Co2(CO)6}2(LiC^CC^CeSiMe3) afforded the diyne dimer
{Co2(CO)6}3{Me3Si(C^C)4SiMe3} [22].
The molecular structures of the lithiated species are gener-
ally unknown with the exception of Berke0s W complex (above),
for which the crystal structure revealed that two Li(thf)2
(d) Alkynyls. The synthesis of {W(CO)3Cp}2C2 from LiC^CH and
WX(CO)3Cp (X ¼ Cl, Br) proceeds via the putative intermediate
LiC^CW(CO)2Cp [11]. Lithiation of Re(C^CH)(NO)(PPh3)Cp
with LiBu gives LiC^CRe(NO)(PPh3)Cp, which reacts with
electrophiles (D2O, MeI, ClSiMe3, ClSnPh3) or with trans-
RhCl(CO)(PPh3)2 and trans-PdCl2(PEt3)2 to give mixed-metal
derivatives [12]. With more than one equivalent of LiBu, both
the ethynyl group and the Cp ring are metallated, as shown by
reactions with MeI or SnClPh3. The analogous Cp*
complex gave only LiC^CRe(NO)(PPh3)Cp* [13]. Reactions of
LiC^CeRe(NO)(PPh3)Cp with W(CO)6, Mn(CO)3Cp0 (Cp0 ¼ Cp,
moieties are also each coordinated in
p-fashion by C^C and
C^O groups [18].
Continuing our studies of diynyl complexes containing Ru(PP)
Cp0 [(PP)Cp0 ¼ (PPh3)2Cp, (dppe)Cp, (dppe)Cp*], we have begun
a study of the deprotonation of the C^CC^CH group with a view to
forming functionalised derivatives (containing either organic or
metallic groups) which cannot easily be obtained from the parent
diynes. The following describes initial studies into the lithiation of
the diynyl ligands, together with some studies of their further
reactions with organic and metal-containing electrophiles. We
have reported reactions between LiC^CC^CRu(dppe)Cp* and 1,2-
C5F6Cl2 to give 1-ClC5F6-2-C^CC^CRu(dppe)Cp* and with the
polyfluoroaromatics C6F5X (X ¼ F, OMe, CN, NO2) and C10F8 during
the course of this work [23].
h
-C5HCl4, h-C5Cl5) and Fe(CO)5, followed by addition of [Me3O]
BF4, gave the corresponding carbene complexes [14].
Lithiation of Fe(C^CH)(dppe)Cp* with LiMe or LiBut and treat-
ment with PClPh2 gave Fe(C^CPPh2)(dppe)Cp*, the dppe ligand
also being metallated with an excess of LiR [15]. Metallation of
2. Results and discussion
M(C^CH)(PP)(L0) [M ¼ Fe, (PP) ¼ dppm, L0 ¼ Cp; M ¼ Ru, L0 ¼ h5
-
C9H7, (PP) ¼ (PMe3)(PPh3), (PPh3)2, dppe] occurs with LiBut
at ꢀ78 ꢁC. All react with MeOTf to give vinylidenes [M(]C]
CMe2)(PP)L0]OTf and with SnClPh3 to give M(C^CSnPh3)(PP)(L0).
2.1. Lithiation of Ru(C^CC^CH)(PP)Cp0 [(PP)Cp0 ¼ (dppe)Cp* 1,
(PPh3)2Cp 2]
With [I(py)2]BF4, Ru(C^CI)(PP)(
h
5-C9H7) [(PP) ¼ (PPh3)2, dppe]
Previous work has shown that lithiation of terminal metalla-
alkynes and metalla-diynes proceeds with strong bases (LiBu,
LiMe, LiBut), although the presence of other electrophiles, such as
CO, can result in preferential attack on these centres [17]. With the
complexes Ru(C^CC^CH)(PP)Cp0 [(PP)Cp0 ¼ (PPh3)2Cp, (dppe)Cp,
(dppe)Cp*] the alternative sites of proton abstraction are the Cp0
groups or the dppe ligand. In some cases, it has been shown that
this problem can be overcome by the use of sterically bulky orga-
nolithiums, such as LDA.
were formed [16].
(e) Diynyls and triynyls. Deprotonation of W(C^CC^CH)(CO)3Cp is
achieved with bulky LDA, smaller LiR reagents attacking the CO
groups. Orange LiC^CC^CW(CO)3Cp reacts with SiClMe3
and MnCl(CO)5 to give the silylated and manganated diynyl
complexes, respectively [17]. The reaction between Li2C4(thf)n
and fac-W(CO)3(dppe)(thf) afforded [Li(thf)2]2[{(dppe)(OC)3W}2
(C^CC^C)] which was successfully employed as a precursor for
novel derivatives containing the W^CC^CC^W moiety [18].
In the present work, we report the lithiation of the diynyl
ligands in Ru(C^CC^CH)(PP)Cp0 [(PP)Cp0 ¼ (dppe)Cp* 1, (PPh3)2Cp
2] using LiBu, LiMe or LDA at ꢀ78 ꢁC (Eq. (1)).
Crude Re(C^CC^CLi)(NO)(PPh3)Cp can be isolated as an
orange solid after reaction of LiBu with Re(C^CC^CH)(NO)(PPh3)
Cp in thf/hexane; subsequent reactions with trans-RhCl(CO)
(PPh3)2 and trans-PdCl2(PEt3)2 gave the expected mixed Re-Rh and
Re-Pd complexes, the latter being accompanied by trans-Pd
{C^CC^C[Re(NO)(PPh3)Cp]}2(PEt3)2 [12b]. Reactions of the lith-
Ru(C^CC^CH)(PP)Cp0 þ LiR / LiC^CC^CRu(PP)Cp0
(1)
The initial bright yellow solution of the metalladiyne rapidly
darkens after addition of the organo-lithium reagent, and we
assume þthat the anion Ru(C^CC^Cꢀ)(PP)Cp (or the ion-pair
[Li(solv) ][Ru(C^CC^Cꢀ)(PP)Cp0]; solv ¼ thf, OEt2) is present in
these solutions. The 31P NMR spectrum of Ru(C^CC^CH)(dppe)
iodiyne with Fe(CO)5, Mn(CO)3(
h
-C5X5) (X ¼ Cl, Br) or Mn(CO)3(
h-
C5H4Cl), followed by [OMe3]BF4, gave the corresponding carbene
complexes, the latter being accompanied by Re(C^CC^CMe)
(NO)(PPh3)Cp [14]. Treatment of Re{(C^C)xH}(NO)(PPh3)Cp*
(n ¼ 2, 3) with CuI in the presence of LiBu afforded Re{(C^C)xCu}
(NO)(PPh3)Cp* [19].
Cp* in thf-d8 at ꢀ78 ꢁC contains a single resonance at
d
80.7. After
82.9.
addition of two equiv. of LiBu, there is now a single peak at
d
The 1H NMR spectrum of the diyne contains a singlet for the CH
proton at 1.34, other resonances for the Cp* ( 1.59), dppe (
2.15e2.17, 2.71e2.76) and Ph groups ( 7.25e7.78) also being
d
d
d
Metallation of Fp*C^CC^CH [Fp* ¼ Fe(CO)2Cp*] with LiBus,
followed by reaction with Fp*Cl, gave Fp*2C4 [20]. Lithio derivatives
of Fe(C^CC^CH)(CO)(L)Cp (L ¼ CO, PPh3) react with SiClMe3 and
MX(CO)3Cp (M ¼ Mo, W) [21].
d
present. After lithiation, minor shifts of ca 0.05 ppm in the latter
peaks are accompanied by a larger shift of the CH resonance to
d
1.68 and a decrease in its relative intensity, suggesting that
Generally it was found that as the carbon chain lengthens, the
lithio derivatives are progressively less nucleophilic and/or basic.
Relative pKa values of W(^CH)(CO)2Tp* [7] and Re(C^CH)(NO)
(PPh3)Cp0 (Cp0 ¼ Cp, Cp*) are 28.7 and 22e34 (all in thf), those of
the Re compounds being higher than analogous organo-lithio
carbons [13].
only partial lithiation had occurred. Addition of an excess of orga-
nolithium reagent resulted in considerable broadening of
this region, precluding further analysis. These small differences
in chemical shifts are not conclusive evidence for metallation
and give no information about the structure of the putative
Ru(C^CC^CeLi)(dppe)Cp* derivative 3.

M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
3475
Table 2
Although we have not been able to characterise these
Selected bond parameters for Ru(C^CC^CR)(dppe)Cp* (R ¼ Me, GePh3).
species directly, addition of electrophiles, such as SiClMe3, to
the lithiated diynyls affords the expected stable silyldiynes
Ru(C^CC^CeSiMe3)(PP)Cp0 [(PP)Cp0 ¼ (dppe)Cp* 4, (PPh3)2Cp 5]
in 60e80% isolated yields. This reaction serves as a means of
assaying the progress of the lithiation under various conditions.
Further exploration of the lithiation of Ru(C^CC^CH)(PP)Cp0 was
achieved by using one or two equiv. LiR (R ¼ Me, Bu, NMe2) and
assaying progress of the reaction by isolation of the
Ru(C^CC^CSiMe3)(PP)Cp0 formed after addition of SiClMe3. Some
results of reactions carried out under a variety of conditions are
given in Table 1. Yields of between 59 and 86% were reproducibly
obtained. The earlier syntheses of the silyldiynes were achieved by
reaction of RuCl(PP)Cp0 with HC^CC^CSiMe3 in thf in the pres-
ence of Na[BPh4] and NEt3 at 50 ꢁC [24].
A limited range of similar experiments was also carried out
using AuCl(PPh3) as the electrophile, isolated yields of Ru
{C^CC^CAu(PPh3)}(PP)Cp0 [(PP)Cp0 ¼ (dppe)Cp* 6, (PPh3)2Cp 7]
ranging between 56 and 85% (Table 2). The gold complexes have
been obtained previously in 93 and 69% yields, respectively, from
reactions between Ru(C^CC^CH)(PP)Cp0 and AuCl(PPh3) in the
presence of K[N(SiMe3)2] in thf at r.t. [24]. We have found that the
“best” conditions for the lithiation of the diynyls involve the
addition of two equivalents of organolithium reagent at ꢀ78 ꢁC in
thf as solvent, followed by warming to room temperature, cooling
again to ꢀ78 ꢁC and addition of the electrophile. Reactions are
completed by a final warming to room temparature prior to work-
up and isolation of the product.
Complex
8
13
ꢀ
Bond distances (A)
RueP(1)
RueP(2)
RueC(cp)
(av.)
2.2616(6)
2.2731(5)
2.236e2.273(2)
2.26
2.2778(7)
2.2726(7)
2.238e2.286(2)
2.259
RueC(1)
2.038(2)
1.150(3)
1.428(3)
1.192(3)
1.474(3)
1.975(3)
1.224(3)
1.377(3)
1.209(3)
1.881(3)
C(1)eC(2)
C(2)eC(3)
C(3)eC(4)
C(4)eX
Bond angles (ꢁ)
P(1)eRueP(2)
P(1)eRueC(1)
P(2)eRueC(1)
RueC(1)eC(2)
C(1)eC(2)eC(3)
C(2)eC(3)eC(4)
C(3)eC(4)eX
82.57(2)
82.53(6)
86.12(5)
178.11(18)
173.7(2)
177.8(2)
176.5(3)
82.73(2)
79.23(7)
89.02(7)
176.5(2)
176.2(3)
179.0(3)
165.5(2)
alkynylsilyl-lithium derivative LiSi(C^CSiMe3)(SiMe2But) (A),
which is a dimer containing one thf molecule attached to one Li
atom, which is also attached to two Si(C^CSiMe3) groups by LieSi
bonds. The second Li atom is also attached to these Si atoms, as well
as being p-bonded to the two C^C triple bonds.
A more relevant interaction is found for the two Li atoms in
[Li(thf)2]2[(dppe)(OC)3W(C^CC^C)W(CO)3(dppe)] (B), which was
obtained from Li2C4(thf)n and fac-W(CO)3(dppe)(thf) [18]. Here,
each Li is tetrahedrally coordinated by two thf ligands and two
type interactions with a C^C triple bond and a CO ligand.
Following these precedents, it is likely that the Li in
LiC^CC^CRu(PP)Cp0 is coordinated to a C^C triple bond, with
further interactions with a solvent molecule (thf) and either the
phosphine or Cp0 ligands
p-
As implied above, we have not been able to isolate the lithiated
diynyleruthenium complexes and so have not been able to deter-
mine their molecular structures by single-crystal XRD studies, for
example. However, two recent examples of lithiated alkynyl
compounds provide some pointers to possible molecular arrange-
ments. Kira et al. [25] have reported the molecular structure of the
Ph2
P
Ph2
P
CO
OC
R2Si
Li
C
C
C
SiMe3
SiMe3
Li
O
OC
W
C
C
C
C
W
CO
R2Si
C
Li
(thf)2
P
C
C
P
Li
(thf)2
Ph2
Ph2
O
O
A
R = SiMe2But
B
Table 1
Lithiation of Ru(C^CC^CH)(PP)Cp0.
LiR
Reagent
Solvent
Temperature/ꢁC
Timea
Yield/% b
(a) Ru(C^CC^CH)(PPh3)2Cp
LiBu (1 eq)
LiBu (1 eq)
LiBu (2 eq)
LiBu (2 eq)
LiMe (1 eq)
LiMe (1 eq)
LDA (1 eq)
SiClMe3
AuCl(PPh3)
SiClMe3
AuCl(PPh3)
SiClMe3
AuCl(PPh3)
SiClMe3
thf/hexane (1/1)
thf/hexane (1/1)
thf
ꢀ40
ꢀ80
ꢀ78
ꢀ78
ꢀ20
ꢀ20
ꢀ78
1 h
1 h
30 min
30 min
1 h
74
62
80
70
74
56
59
thf
thf/hexane (2/1)
thf/Et2O (1/1)
thf
1 h
2 h
(b) Ru(C^CC^CH)(dppe)Cp*
LiBu (1 eq)
LiBu (1 eq)
LiBu (2 eq)
LiBu (2 eq)
SiClMe3
AuCl(PPh3)
SiClMe3
AuCl(PPh3)
SiClMe3
SiClMe3
AuCl(PPh3)
SiClMe3
AuCl(PPh3)
thf
thf
thf
thf
ꢀ78
ꢀ78
ꢀ78
ꢀ78
ꢀ80
0
ꢀ20
ꢀ80
ꢀ78
1 h
78
60
86
85
64
70
64
75
62
30 min
30 min
30 min
2 h
30 min
30 min
1 h
LiBu/tmeda (1 eq)
LiMe (2 eq)
thf/hexane (2/1)
thf/hexane (1/1)
thf/hexane (2/1)
thf/Et2O (1/1)
thf/hexane (1/1)
LiMe (2 eq)
LiBut (1 eq)
LDA
1 h
a
After this time at the indicated temperature, the mixture was allowed to warm to r.t.
Isolated yield of product.
b

3476
M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
O
[Ru*]
C
C
C
C
CH3
[Ru*]
C
C
C
C
C
R
8
70%
O
R = Me 9 60%;
Ph 10 75%
MeI
R
Cl
Li
[Ru*]
C
C
C
C
O
O
Ph
H
Me
Cl
OH
O
[Ru*]
C
C
C
C
C
[Ru*]
C
C
C
C
C
H
Ph
Me
12 76%
11 40%
[Ru*] = Ru(dppe)Cp*
Scheme 1. Some reactions of Li-C^CC^C-Ru(dppe)Cp* with organic electrophiles.
The reactivity of the lithiated metalla-diynes was initially
examined in a series of reactions with organic electrophiles on
the one hand (Scheme 1), and with various metal halides on
the other (Scheme 2). We have used the Ru(dppe)Cp* as an
electron-rich end-group for the various diynes, so that the
work described below is largely limited to this system.
However, related studies have shown that the Ru(PPh3)2Cp
end-group
affords
similar
complexes
with
trans-
RhCl(CO)(PPh3)2 and {CuCl(PPh3)}4, also described below
(Scheme 3).
[Ru*]
[Ru*]
C
C
C
C
Au
Au
PPh2
PPh2
[Ru*]
C
C
C
C
MR3
MR3 = SiMe3 4 64-86%; GeMe3 13 82%;
SnPh3 14 70%
C
C
C
C
MClR3
17 90%
(AuCl)2(µ-dppm)
MR3 = SiMe3, GeMe3,
SnPh3
[Ru*]
C
C
C
C
Li
PtCl2(PPh3)2
AuCl(PPh3)
Au(PPh3)
PPh3
Pt
PPh3
[Ru*]
C
C
C
C
Cl
[Ru*]
C
C
C
C
15 40%
6
60-85%
[Ru*] = Ru(dppe)Cp*
Scheme 2. Some reactions of LieC^CC^CeRu(dppe)Cp* with metal halides.

M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
3477
PPh3
Rh
[Ru]
C
C
C
C
SiMe3
[Ru]
C
C
C
C
CO
PPh3
5
trans-RhCl(CO)(PPh3)2
18 50%
SiClMe3
[Ru]
C
C
C
C
Li
AuCl(PPh3)
Au(PPh3)
{CuCl(PPh3)}4
[Ru]
C
C
C
C
[Ru]
C
C
C
C
Cu(PPh3)
19 40%
7
[Ru] = Ru(PPh3)2Cp
Scheme 3. Reactions of Ru(C^CC^CLi)(PPh3)2Cp with trans-RhCl(CO)(PPh3)2 and {CuCl(PPh3)2}.
75% yield. Characteristic spectroscopic data include
2000, 2109 cmꢀ1 and
n
(C^C) at
2.2. Reactions of Li-C^CC^C-Ru(dppe)Cp* 3
n
(CO) at 1716 cmꢀ1, the latter group
giving a singlet 13C resonance at dC 206.41. The ES-MS contains
Spectroscopic properties of the Ru(dppe)Cp* fragment resemble
those reported on numerous other occasions. In particular, the 1H,
13C and 31P NMR spectra contain resonances assigned to Cp* [dH ca
1.50, dC ca 10.00 (Me), ca 93.00 (ring C), and dP ca 81.00 (dppe)].
Resonances between dC 52 and 125 arise from C atoms in the C4
chain, that with highest chemical shift being assigned to the
RueC(1)^ atom, and other signals with progressively lower
chemical shift to C(2), C(3) and C(4) (numbering from the Ru atom),
i.e., with increasing distance from the metal centre. Limited solu-
bilities precluded our observing 13C resonances for the C4 chains in
some cases. Other data arising from the functional groups are given
in the separate discussions below.
M
þ and [M þ Na]þ at m/z 788 and 811, respectively.
(d) ClC(O)OMe. The reaction of Ru(C^CC^CLi)(dppe)Cp* with methyl
chloroformate afforded Ru{C^CC^CC(O)OMe}(dppe)Cp* 11 in
40% yield, the OMe group giving a singlet resonance at dH 1.68, at
somewhat higher field than normal, and n
(CO) at 1723 cmꢀ1 in the
IR spectrum; this complex is somewhat unstable in solution and
neither a satisfactory microanalysis nor a 13C NMR spectrum could
be obtained. The ES-MS spectrum contains Mþ at m/z 742.
(e) PhCHO. The reaction of benzaldehyde with 3 gave bright
orange Ru{C^CC^CCHPh(OH)}(dppe)Cp* 12, distinguished by
singlet CH and OH resonances at dH 1.66 and 5.52, respectively.
The CHPh(OH) group gives rise to a singlet at dC 79.89. In the
ES-MS, Mþ and [M þ Na]þ are found at m/z 790 and 813,
respectively.
2.3. Reactions with organic substrates
(a) MeI. The reaction of MeI with a solution of Ru(C^CC^CLi)(dppe)
Cp* in thf at ꢀ78 ꢁC afforded Ru(C^CC^CMe)(dppe)Cp* 8 in 70%
yield after conventional work-up. In addition to characteristic
peaks for the Ru(dppe)Cp* fragment, the Me group gave singlet
resonances at dH 1.73 and dC 21.03, while the 13C NMR spectrum
also contained resonances at dC 52.46, 76.86, 91.73 and 124.69,
2.4. Reactions with metal halides
(a) GeCl(PPh3) and SnCl(PPh3). Following the ready synthesis of
Ru(C^CC^CSiMe3)(dppe)Cp* 4 during the assay experiments
described above, reactions of the lithio-diyne with other Group
14 halides were attempted. Reactions with GeClPh3 and
SnClPh3 afforded Ru(C^CC^CEPh3)(dppe)Cp* (E ¼ Ge 13, Sn
14) in 82 and 70% yields, respectively. Characterisation fol-
lowed from their spectra (see Section 4) and the presence of
ions at m/z 1009 ([M þ Na]þ) and 988 ([M þ H]þ) (for 13), and
1033 (Mþ) (for 14). The molecular structure of 13 was
confirmed by a single-crystal X-ray diffraction study (below).
(b) cis-PtCl2(PPh3)2. A similar reaction between Ru(C^CC^CeLi)
(dppe)Cp* and cis-PtCl2(PPh3)2 afforded {Cp*(dppe)Ru}C^
CC^C{trans-PtCl(PPh3)2} 15 in 40% yield. Spectroscopic data
assigned to the carbons of the C4 chain. Two n(C^C) bands at
1908, 2029 cmꢀ1 are in the IR spectrum, while the electrospray
mass spectrum (ES-MS) contains [M þ MeOH]þ at m/z 730. The
molecular structure of 8 has been determined by a single-crystal
X-ray diffraction study (below).
(b) MeC(O)Cl. Bright yellow Ru{C^CC^CC(O)Me}(dppe)Cp* 9 was
obtained from the reaction between acetyl chloride and
Ru(C^CC^CLi)(dppe)Cp* in 60% yield. The Me group gives
resonances at dH 2.14, dC 33.35, with the carbonyl group giving
a singlet at dC 201.57. The IR spectrum contains
n(C^C) at 2004,
2048 and
n
(CO) at 1710 cmꢀ1, with Mþ at m/z 726 in the ES-MS.
(c) PhC(O)Cl. An immediate colour change from yellow
to red occurs when benzoyl chloride is added to
Ru(C^CC^CeLi)(dppe)Cp* in thf at ꢀ78 ꢁC. The usual work-up
afforded Ru{C^CC^CC(O)Ph}(dppe)Cp* 10 as a red powder in
include a broad resonance between d 6.83e8.02 arising from
the ten Ph groups, while the 31P NMR spectrum contains two
equal intensity resonances at dP 81.9 (dppe) and 22.2 (PPh3);
the Pt satellites of the latter resonance were not resolved.

3478
M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
The ES-MS contained Mþ at m/z 1437. No other tractable
products were obtained.
(c) {CuCl(PPh3)}4. Extending the synthetic route to other Group 11
metals, the reaction between Ru(C^CC^CLi)(dppe)Cp* and
{CuCl(PPh3)}4 was found to give the Ru2C8 complex, {Ru(dppe)
Cp*}2(
of this complex was from microanalysis and spectroscopic data,
including IR [
(C^C) at 1949, 2101 cmꢀ1] and Mþ at m/z 1366
m-C^CC^CC^CC^C) 16, in 85% yield. Characterisation
n
in the ES-MS, together with an XRD molecular structure
determination which has been reported previously on another
occasion. In all cases, the data are identical with those obtained
from an authentic sample [26].
While the exact mechanism of formation of this copper-free
derivative was not determined, a likely route involves the oxida-
tive coupling of the lithio reagent, possibly via a radical interme-
diate. Previous syntheses of binuclear C8 complexes have
proceeded from either the chloro-metal complex and
Me3Si(C^C)4SiMe3 in the presence of KF and wet MeOH, or by
oxidative coupling of Ru(C^CC^CH)(dppe)Cp* [with CuI/tmeda;
Hay conditions] [26].
Fig. 2. Plot of the molecule of 13 projected onto the plane of the Cp* ring, showing
atom numbering scheme.
shaped geometry [28], it is likely that the steric bulk of the
Ru(dppe)Cp* fragments precludes this geometry for 17.
(d) (AuCl)2(
{Au(C^CC^CH)}2(
HC^CC^CH under Cadiot-Chodkiewicz conditions, while the
tetrametallic derivative {Cp(OC)3WC^CC^CAu}2( -dppm) was
similarly formed from W(C^CC^CH)(CO)3Cp and (AuCl)2(
dppm) [27]. The related ruthenium complex {Cp*(dppe)
RuC^CC^CAu}2( -dppm) 17 could not be prepared in this
manner. However, addition of (AuCl)2( -dppm) to two equiv.
Ru(C^CC^CLi)(dppe)Cp* generated in thf in situ afforded 17 in
m
-dppm). We have previously described the synthesis of
m
-dppm) from (AuCl)2( -dppm) and
m
2.5. Reactions of Ru(C^CC^CLi)(PPh3)2Cp
m
m-
(a) trans-RhCl(CO)(PPh3)2. The complex {Cp(PPh3)2Ru}(C^CC^C)
{Rh(CO)(PPh3)2} 18 was obtained from the reaction of
Ru(C^CC^CH)(PPh3)2Cp treated with n-BuLi at ꢀ78 ꢁC, fol-
lowed by adddition of one equivalent of trans-RhCl(CO)(PPh3)2.
Complex 18 displayed all expected resonances in the 1H, 31P
NMR analysis, IR, microanalysis and ES-MS. In the 1H and 31P
NMR spectra, the characteristic peaks for the Ru(PPh3)2Cp and
Rh(CO)(PPh3)2 groups are present, the PPh3 ligands being
distinguished in the 31P NMR spectrum by resonances at dP 38.5
m
m
90% yield. Characterisation followed from IR [n(C^C) at 1982,
2106 cmꢀ1], 1H and 31P NMR spectroscopy (particularly two
resonances at dP 82.0, 35.6, relative intensities 2:2, assigned to
dppe and dppm ligands, respectively). The 13C NMR spectrum
contains resonances assigned to the Cp*, dppm and dppe ligands,
but none of the C4 chain signals were found. The ES-MS contains
(Rh) and 50.6 (Ru). In the IR spectrum, two
n
(C^C) bands at
1978 and 1955 cmꢀ1 and one
n
(CO) band at 2108 cmꢀ1 were
[MeH]þ at m/z 2143. Although{Au(C^CBut)}2(
m-dppm) has a U-
observed. The ES-MS of 18 contains Mþ at m/z 1394 and frag-
ment ions at m/z 429 and 691 for [Ru(PPh3)nCp]þ (n ¼ 1, 2,
respectively).
(b) {CuCl(PPh3)}4 Lithiation of Ru(C^CC^CH)(PPh3)2Cp 2 and
addition of {CuCl(PPh3)}4 afforded {Cp(Ph3P)2Ru}C^CC^C
{Cu(PPh3)} 19, characterised by elemental microanalysis, the IR,
1H and 31P NMR spectra (particularly in the latter, with 2:1
resonances at dP 38.5 and 50.8, assigned to the CuePPh3 and
RuePPh3 ligands, respectively) and [M þ MeOH]þ at m/z 1096
in the ES-MS.
2.6. Molecular structures
The molecular structures of 8 and 13 have been determined
from single-crystal X-ray diffraction studies with plots of single
molecules of each complex being given in Figs.1 and 2, respectively,
non-hydrogen atoms being drawn with 50% probability ellipsoids.
Selected bond parameters are listed in Table 2. Structural parame-
ters are similar to those found in many other compounds con-
taining the distorted octahedral Ru(dppe)Cp* fragment [RueP(1,2)
ꢀ
2.2616(6)e2.2778(7), RueC(cp) (av.) 2.26 A], while the diynyl
ligand has the expected shortelongeshort CeC bond alternation
[(values for 8/13) RueC(1) 2.038(2)/1.975(3); C(1)eC(2) 1.150(3)/
1.224(3); C(2)eC(3) 1.428(3)/1.377(3); C(3)eC(4) 1.192(3)/1.209(3),
ꢀ
C(4)eC(5) (8)/C(4)eGe (13) 1.474(3)/1.881(3) A]. Angles at Ru
Fig. 1. Plot of the molecule of 8 projected onto the plane of the Cp* ring, showing atom
numbering scheme.
confirm the near octahedral distribution of ligands [P(1)eRueP(2)

M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
3479
82.57(2)/82.73(2), P(1,2)eRueC(1) 79.23(7)e89.02(7)ꢁ] while the
4.3. Reagents
C4 chain is close to linear [RueC(1)eC(2) 178.11(18)/176.5(2); C(1)e
C(2)eC(3) 173.7(2)/176.2(3); C(2)eC(3)eC(4) 177.8(2)/179.0(3);
C(3)eC(4)eX [X ¼ C(5) (8)/Ge(1) (13) 176.5(3)/165.5(2)ꢁ]. Interest-
ingly, there appears to be significantly greater degree of delocali-
sation along the RueC4eGe chains than found for the analogous
RueC4eMe derivative.
Ru(C^CC^CH)(PP)Cp0 [(PP)Cp0 ¼ (PPh3)2Cp, (dppe)Cp* [24]],
(AuCl)2(m-dppm) [28,30], trans-RhCl(CO)(PPh3)2 [31], cis-
PtCl2(PPh3)2 [32], {CuCl(PPh3)}4 [33] and AuCl(PPh3) [34] were
prepared as previously described. Organolithium reagents [LiMe.-
LiBr, 1.5 M solution in Et2O; LiBu, 1.6 M or 2.3 M solutions in
hexanes, or 1.045 M solution in thf; LiBut,1.6 M solution in heptane]
were obtained from Aldrich; LDA was made from LiBu in hexanes
and NHMe2. Other reagents were commercial samples from Aldrich
or Fluka and were used as received.
3. Conclusions
The reactions described above (summarised in Schemes 1e3)
show that the lithiated metalla-diyne Ru(C^CC^CLi)(dppe)Cp* 3
is a powerful nucleophilic reagent suitable for preparing a wide
range of diynyl complexes containing either functional organic
groups or other metal-ligand groups. Some of the products can be
obtained from the parent diynes, or by transformation of other
functional diynyl complexes, but most are new compounds which
have not been obtained by more usual approaches. The difference
in reactivity of the two lithiated intermediates with {CuCl(PPh3)}4
may be the result of oxidation of the more electrophilic Ru(dppe)
Cp* derivative; at this time, we have not pursued this matter
further.
We note that attack at the CO group does notoccur in the reactions
which afford 9, 10 and 11, thus (under these conditions at least)
precluding access to complexes containing longer carbon chains into
which aCRgrouphas beenformallyinserted. Similarly, inthereaction
with cis-PtCl2(PPh3)2, there was no evidence for the replacement of
the second Cl atom to form disubstituted complex, which would have
contained an interesting RueC4ePteC4eRu array. Further work on
compounds of these types will be presented elsewhere.
4.4. Lithiation experiments
(a) SiClMe3.
(i) A solution of Ru(C^CC^CH)(dppe)Cp* 1 (50 mg, 0.07 mmol)
in thf (5 ml) was treated with LiBu (140 ml, 1.045 M solution in
thf) at ꢀ78 ꢁC and stirrred for 30 min. An aliquot of SiClMe3
(18 ml, 0.14 mmol) was added and the reaction mixture was
allowed to warm to r.t. over 2 h. Solvent was removed to give
a yellow residue which was then dissolved in hexane (70 ml),
filtered via cannula and evaporated to dryness to give
Ru(C^CC^CSiMe3)(dppe)Cp* 4 (47 mg, 86%) as a bright
yellow powder, identified by comparison with literature data.
1H NMR (C6D6):
1.81e1.88, 2.52e2.56 (2 ꢃ m, 2 ꢃv2H, dppe-CH2), 7.02e7.87
d 0.29 (s, 9H, SiMe3), 1.56 (s, 15H, Cp*),
(m, 20H, Ph). 31P NMR:
d
81.3 (s, dppe). Lit. values [24]: 1H
NMR (C6D6):
NMR: 81.3.
d
0.23, 1.53, 1.78e2.49 (2 ꢃ m), 6.89e7.86. 31P
d
(ii) Similarly, from Ru(C^CC^CH)(PPh3)2Cp
2
(51 mg,
The new compounds are characterised spectroscopically, all
showing the expected IR absorptions or NMR resonances, while the
ES-MS contain molecular ions, or adducts with solvent or other ions
present. Common features include the [Ru(PPh3)nCp]þ (n ¼ 1, 2)
ions (at m/z 429 and 635, respectively) or [Ru(dppe)Cp*]þ at m/z
651. The molecular structures of two examples (8 and 13) have been
confirmed by single-crystal XRD structure determinations, from
which it is apparent that replacement of Me (in 8) by GePh3 (in 13)
results in some delocalisation along the C4 chain.
0.07 mmol) and SiClMe3 (17 ml, 0.14 mmol) was obtained
Ru(C^CC^CSiMe3)(PPh3)2Cp 5 (45mg, 80%) as a bright
yellow powder. 1H NMR (CDCl3):
d
0.28 (s, 9H, SiMe3), 4.36
(s, 5H, Cp), 6.91e7.59 (m, 30H, Ph). 31P NMR:
50.8 (s, PPh3).
Lit. values [24]: 1H NMR (CDCl3): 0.26, 4.30, 6.92e7.58. 31
NMR: 50.7.
(b) AuCl(PPh3).
d
d
P
d
(i) Similar lithiation of Ru(C^CC^CH)(dppe)Cp* (51 mg,
0.07 mmol) and treatment with AuCl(PPh3) (39 mg, 0.07
mmol) afforded bright yellow Ru{C^CC^CAu(PPh3)}
4. Experimental
(dppe)Cp* 6 (72 mg, 85%). 1H NMR (C6D6):
d
1.54 (s, 15H, Cp*),
2.14e2.20, 2.73e2.76 (2 ꢃ m, 2 ꢃ 2H, dppe-CH2), 6.96e7.86
(m, 35H, Ph). Lit. values [24]: (C^C) 2119m, 2072m,
1981w cmꢀ1
dH 1.52 (Cp*).
4.1. General
n
;
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
nitrogen and degassed before use. Separations were carried out by
preparative thin-layer chromatography on glass plates
(20 ꢃ 20 cm2) coated with silica gel (Merck, 0.5 mm thick).
(ii) Similarly, lithiated Ru(C^CC^CH)(PPh3)2Cp (51 mg, 0.07
mmol) and AuCl(PPh3) (68 mg, 0.14 mmol) gave bright
yellow Ru{C^CC^CAu(PPh3)}(PPh3)2Cp 7 (57 mg, 70%). IR
(Nujol)/cmꢀ1: v(C^C) 1983m, 2073m. 1H NMR (CDCl3):
d
4.40 (s, 5H, Cp), 6.86e7.64 (m, 45H, Ph). 31P NMR (CDCl3):
d
33.9 (s, 1P, Au-PPh3), 51.2 (s, 2P, Ru-PPh3). Lit. values [24]:
IR/cmꢀ1
:
n
(C^C) 2116m, 2073m, 1982m cmꢀ1
;
1H NMR
4.2. Instruments
(CDCl3): d d 32.5, 49.9.
4.28, 7.08e7.59. 31P NMR:
IR spectra: Bruker IFS28 FT-IR spectrometer. Nujol mull spectra
were obtained from samples mounted between NaCl discs. NMR
spectra: Varian 2000 instrument (1H at 300.13 MHz, 13C at
75.47 MHz, 31P at 121.503 MHz) at 298 K. Samples were dissolved in
CDCl3 or C6D6 contained in 5 mm sample tubes. Chemical shifts are
given in ppm relative to internal tetramethylsilane for 1H and 13C
NMR spectra and external H3PO4 for 31P NMR spectra. Electrospray
mass spectra (ES MS; positive-ion mode): Fisons Platform II spec-
trometer. Solutions in MeOH or MeCN were injected into a via
a 10 ml injection loop; nitrogen was used as the drying and nebu-
lising gas. Chemical aids to ionisation were used as required [29].
Elemental analyses were by CMAS, Belmont, Vic. 3216, Australia.
4.5. Reactions of Ru(C^CC^CLi)(dppe)Cp* 3 with organic
electrophiles
(a) MeI.
A
solution of Ru(C^CC^CH)(dppe)Cp* (50 mg,
0.07 mmol) in thf (5 ml) at ꢀ78 ꢁC was treated with LiBu (91
m
m
l,
l,
1.6 M solution in hexanes). After stirring for 30 min, MeI (32
0.51 mmol) was added and the mixture was allowed to warm
to r.t. over 3 h. Removal of solvent, extraction with hexane
(60 ml), filtration via cannula and evaporation to dryness gave
Ru(C^CC^CMe)(dppe)Cp* 8 (40 mg, 70%) as a bright yellow
powder. Single crystals suitable for the X-ray study were

3480
M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
obtained from CH2Cl2/hexane. Anal. Calcd (C41H42P2Ru): C,
70.47; H, 6.06; M, 700. Found: C, 70.45; H, 5.99. IR (CH2Cl2)/
cmꢀ1 (C^C) 1908m, 2029m. 1H NMR (C6D6):
1.60 (s, 15H,
Cp*), 1.73 (s, 3H, Me), 1.87e2.01, 2.62e2.65 (2 ꢃ m, 2 ꢃ 2H,
dppe), 6.89e7.28 (m, 20H, Ph). 13C NMR:
10.12 (C5Me5), 21.03
solution in hexanes) at ꢀ78 ꢁC and stirred for 30 min. GeClPh3
(31 mg, 0.07 mmol) was added and the mixture was allowed to
warm to r.t. over 3 h. Solvent was removed and the yellow
residue was extracted with hexane (60 ml) and filtered via
cannula. Removal of solvent from the filtrate gave
Ru(C^CC^CGePh3)(dppe)Cp* 13 (62 mg, 82%) as a yellow
crystalline powder. Single crystals suitable for X-ray studies
were grown from thf/hexane. Anal. Calcd (C58H54GeP2Ru): C,
70.60; H, 5.52; M, 987. Found: C, 70.61; H, 5.55. IR (Nujol)/
:
n
d
d
(Me), 29.27e29.88 (m, CH2), 93.25 (C5Me5), 52.46, 76.86, 91.73,
124.69 [4 ꢃ s, C(4), C(3), C(2), C(1)], 127.42e133.96 (m, Ph). 31P
NMR:
d
81.6 (s, dppe). ES-MS (MeOH)/m/z: 731, [M þ MeOH]þ;
635, [Ru(dppe)Cp*]þ.
(b) MeC(O)Cl. From a similar reaction using Ru(C^CC^CH)(dppe)
Cp* (50 mg, 0.07 mmol), LiBu (64 l, 2.3 M solution in hexanes)
and acetyl chloride (26 l, 0.36 mmol), addition of hexane
cmꢀ1
Cp*), 1.75e1.792.50e2.53 (2 ꢃ m, 2 ꢃ 2H, dppe-CH2), 6.89e7.85
(m, 35H, Ph). 13C NMR:
10.17 (s, C5Me5), 29.62e30.12 (dppe-
CH2), 93.22 (C5Me5), 62.40, 86.85, 93.46, 99.42 [4 ꢃ s, C(4), C(3),
: n d 1.56 (s, 15H,
(C^C) 2000m, 2106m. 1H NMR (C6D6):
m
m
d
(20 ml) dropwise to the reaction mixture afforded Ru
{C^CC^CC(O)Me}(dppe)Cp* 9 (34 mg, 60%) as a bright yellow
crystalline powder. Anal. Calcd (C42H42OP2Ru): C, 69.40; H,
C(2), C(1)], 127.64e137.76 (m, Ph). 31P NMR:
d 81.0 (s, dppe). ES-
MS (MeCN)/m/z: 1009, [M þ Na]þ; 988, [M þ H]þ; 675, [Ru(N-
5.83; M, 725. Found: C, 69.36; H, 5.92. IR (Nujol)/cmꢀ1
:
n
(C^C)
1.58 (s, 15H,
Cp*), 2.14 (s, 3H, Me), 1.78e1.85, 2.61e2.68 (2 ꢃ m, 2 ꢃ 2H,
dppe), 7.02e7.23 (m, 20H, Ph). 13C NMR:
10.83 (C5Me5),
CMe)(dppe)Cp*]þ; 635, [Ru(dppe)Cp*]þ.
2004m, 2048m;
n
(CO) 1710m. 1H NMR (C6D6):
d
(b) SnClPh3. Similarly, from Ru(C^CC^CH)(dppe)Cp* (50 mg,
0.07 mmol) and SnClPh3 (45 mg, 0.11 mmol) was obtained
Ru(C^CC^CSnPh3)(dppe)Cp* 14 (54 mg, 70%) as a yellow
crystalline powder. Anal. Calcd (C58H54P2RuSn): C, 67.45; H,
d
30.13e30.83 (m, dppe), 33.35 (s, Me), 94.38 (C5Me5), 90.15,
102.13, 118.52, 121.86 [4 ꢃ s, C(4), C(3), C(2), C(1)],
5.27; M, 1033. Found: C, 67.97; H, 5.51. IR (Nujol)/cmꢀ1
:
n
(C^C)
1.56 (s, 15H, Cp*), 1.78e1.81,
2.52e2.55 (2 ꢃ m, 2 ꢃ 2H, dppe-CH2), 7.01e7.89 (m, 35H, Ph).
13C NMR:
10.21 (s, C5Me5), 29.86e30.01 (m, dppe-CH2), 91.87
(s, C5Me5), 74.82, 86.85, 99.05, 103.22 [4 ꢃ s, C(4), C(3), C(2),
126.96e134.51 (m, Ph), 201.57 (CO). 31P NMR:
d
81.7 (s, dppe).
1977m, 2081m. 1H NMR (C6D6):
d
ES-MS (MeOH)/m/z: 725, Mþ; 635, [Ru(dppe)Cp*]þ.
(c) PhC(O)Cl. Similarly, Ru(C^CC^CH)(dppe)Cp*
0.07 mmol), benzoyl chloride (17
(50 mg,
d
ml, 0.14 mmol) gave Ru
{C^CC^CC(O)Ph}(dppe)Cp* 10 as a red powder (43 mg, 75%).
Anal. Calcd (C47H44OP2Ru): C, 71.65; H, 5.63; M, 788. Found: C,
C(1)], 127.84e134.02 (m, Ph). 31P NMR:
d 81.2 (s, dppe). ES-MS
(MeCN)/m/z: 1033, Mþ; 675, [Ru(NCMe)(dppe)Cp*]þ; 635,
71.76; H, 5.60. IR (Nujol)/cmꢀ1
: n(C^C) 2000m, 2109m; n(CO)
[Ru(dppe)Cp*]þ.
1716m. 1H NMR (C6D6):
d
1.51 (s, 15H, Cp*), 2.08e2.18,
(c) cis-PtCl2(PPh3)2. Similarly, the reaction of lithiated
Ru(C^CC^CH)(dppe)Cp* (50 mg, 0.07 mmol) and cis-
PtCl2(PPh3)2 (59 mg, 0.07 mmol) gave {Cp*(dppe)Ru}C^CC^C
{PtCl(PPh3)2-trans} 15 (43 mg, 40%) as a bright yellow powder.
Anal. Calcd (C76H69ClP4PtRu): C, 63.48; H, 4.84; M, 1437. Found:
2.50e2.54 (2 ꢃ m, 2 ꢃ 2H, dppe), 7.05e7.28 (m, 25H, Ph). 13C
NMR:
d 10.02 (s, C5Me5), 29.23e30.12 (m, dppe), 94.13 [t,
J(CP) ¼ 2 Hz, C5Me5], 63.08, 95.59, 101.00, 112.17 [4 ꢃ s, C(4),
C(3), C(2), C(1)], 127.63e133.63 (m, Ph), 206.41 (s, CO). 31P
NMR:
d
80.5 (s, dppe). ES-MS (MeOH)/m/z: 811, [M þ Na]þ; 788,
C, 63.60; H, 5.81. IR (Nujol)/cmꢀ1
:
n
(C^C) 1984m, 2105m. 1H
1.54(s,15H, Cp*),1.84e1.90 (2 ꢃ m, 2 ꢃ 2H, dppe-
Mþ; 635, [Ru(dppe)Cp*]þ.
NMR (C6D6):
d
(d) ClC(O)OMe. Similarly, from Ru(C^CC^CH)(dppe)Cp* (51 mg,
CH2), 6.83e8.02 (m, 50H, Ph). 31P NMR (C6D6):
d 22.2 (s, 2P, Pt-
0.07 mmol) and methyl chloroformate (12
obtained Ru{C^CC^CC(O)OMe}(dppe)Cp* 11 (20 mg, 40%) as
a yellow powder. IR (Nujol)/cmꢀ1
(C^C) 1971m, 2008m;
(CO) 1723m. 1H NMR (C6D6):
1.53 (s, 15H, Cp*), 1.68 (s, 3H,
Me), 2.06e2.13, 2.38e2.43 (2 ꢃ m, 2 ꢃ 2H, dppe), 7.02e7.26 (m,
ml, 0.15 mmol) was
PPh3), 81.9 (s, 2P, Ru-dppe). ES-MS (MeOH)/m/z: 1437, Mþ;
1436, [M ꢀ H]þ; 635, [Ru(dppe)Cp*]þ.
:
n
(d) {CuCl(PPh3)}4. A solution of Ru(C^CC^CH)(dppe)Cp* 1
n
d
(51 mg, 0.07 mmol) in thf (2 ml) was treated with LiBu (140 ml,
1.045 M solution in thf) at ꢀ78 ꢁC and stirred for 30 min. A
solution of {CuCl(PPh3)}4 (28 mg, 0.07 mmol) in thf (5 ml) was
then added via cannula and the mixture was allowed to warm
to r.t. over 3 h. The resulting red-orange precipitate was
20H, Ph). 31P NMR:
d 80.6 (s, dppe). ES-MS (MeOH)/m/z: 743,
Mþ; 635, [Ru(dppe)Cp*]þ. No satisfactory microanalysis or 13C
NMR spectrum could be obtained for this unstable complex.
(e) PhCHO. Benzaldehyde (15
ml, 0.14 mmol) was added to lithiated
collected and washed with hexane to give {Ru(dppe)Cp*}2(m-
Ru(C^CC^CH)(dppe)Cp* (50 mg, 0.07 mmol) in thf (5 ml) and
the mixture was stirred for 30 min. Addition of water (1 ml),
warming to r.t. over 2 h and removal of solvent gave a yellow
residue. Extraction with hexane (60 ml), filtration via cannula
and evaporation afforded Ru{C^CC^CCHPh(OH)}(dppe)Cp* 12
(44 mg, 76%) as a bright orange crystalline powder. Anal. Calcd
(C47H46OP2Ru): C, 71.37; H, 5.87; M, 790. Found: C, 70.92; H, 5.87.
C^CC^CC^CC^C) 16 (86 mg, 85%). Single crystals suitable
for an X-ray study were grown from CH2Cl2/hexane. The
compound was also identified by comparison with an
authentic sample [27].
(e) (AuCl)2(m-dppm). A solution of Ru(C^CC^CH)(dppe)Cp*
(100 mg, 0.15 mmol) in thf (5 ml) was treated with LiBu (140 ml,
1.045 M solution in thf) at ꢀ78 ꢁC and stirred for 1 h. (AuCl)2(
m-
IR (Nujol)/cmꢀ1
(C6D6):
:
n(OH) 3303w,
n
(C^C) 2000m, 2106m. 1H NMR
dppm) (60 mg, 0.07 mmol) was added and the resulting yellow
precipitate was collected, washed with hexane and dried to
d
1.57 (s, 15H, Cp*), 1.66 (s, 1H, CH), 1.74e1.80, 2.56e2.58
(2 ꢃ s, 2 ꢃ 2H, dppe), 5.52 (s,1H, OH), 7.03e7.29 (m, 25H, Ph). 13C
give {Au(C^CC^C [Ru(dppe)Cp*])}2(
90%). Anal. Calcd (C105H100Au2P6Ru2): C, 58.83; H, 4.70; M,
2144. Found: C, 58.88; H, 4.75. IR (Nujol)/cmꢀ1
(C^C) 982m,
2106m. 1H NMR (C6D6):
1.56 (s, Cp*), 1.81e1.92, 2.80e2.89
(2 ꢃ m, 2 ꢃ 2H, dppe-CH2), 3.23 (s, 2H, dppm-CH2), 6.85e7.97
(m, 60H, Ph). 13C NMR:
10.08 (C5Me5), 29.86e30.12 (dppe-
CH2), 43.33 (dppm-CH2), 93.12 (C5Me5), 127.64e133.76 (m, Ph).
m-dppm) 17 (135 mg,
NMR:
d 10.07 (s, C5Me5), 29.29e29.90 (m, dppe), 79.89 (s, CH),
93.24 (s br, C5Me5), 65.85, 88.72, 99.22,122.10 [4s, C(4), C(3), C(2),
: n
C(1)], 127.68e133.74 (m, Ph). 31P NMR:
d
81.3 (s, dppe). ES-MS
d
(MeOH)/m/z: 813, [M þ Na]þ; 790, Mþ; 635, [Ru(dppe)Cp*]þ.
d
31P NMR:
d 35.6 (s, 2P, dppm), 82.0 (s, 2P, dppe). ES-MS (MeCN)/
4.6. Reactions of Ru(C^CC^CLi)(dppe)Cp* with metal halides
(a) GeClPh3. A solution of Ru(C^CC^CH)(dppe)Cp* 1 (50 mg,
m/z: 2143, [M ꢀ H]þ; 1460, [M ꢀ C4Ru(dppe)Cp*]þ; 1366,
[M ꢀ Au2(dppm)]þ;
675,
[Ru(NCMe)(dppe)Cp*]þ;
635,
[Ru(dppe)Cp*]þ.
0.07 mmol) in thf (5 ml) was treated with LiBu (50 ml, 2.3 M

M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
3481
4.7. Reactions of Ru(C^CC^CLi)(PPh3)2Cp
Supplementary material
(a) trans-RhCl(CO)(PPh3)2. Similarly, {Cp(PPh3)2Ru}(C^CC^C)
{Rh(CO)(PPh3)2} 18 was obtained as a yellow powder (49 mg,
50%) from the reaction between lithiated Ru(C^CC^CH)
(PPh3)2Cp (53 mg, 0.07 mmol) and trans-RhCl(CO)(PPh3)2
(49 mg, 0.07 mmol). Anal. Calcd. (C82H65OP4RhRu): C, 70.64; H,
Full details of the structure determinations (except structure
factors) have been deposited with the Cambridge Crystallographic
Data Centre as CCDC 716005 (8), 716006 (13). Copies of this infor-
mation may be obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB21EZ, UK (Fax: þ 441223 336 033; e-mail:
deposit@ccdc.cam.ac.uk or website: http://www.ccdc.cam.ac.uk).
4.70. Found: C, 70.73; H, 4.76. IR (CH2Cl2, cmꢀ1):
(m),
(CO) 1978 (m), 1955 (m). 1H NMR (C6D6):
n
(C^C) 2108
n
d 7.17e6.92 (m,
60H, Ph); 4.35 (s, 5H, Cp). 31P NMR (C6D6):
d 50.6 (s, Ru(PPh3)2),
38.5 (s, Rh(PPh3)2). ES-MS (MeOH)/m/z: 1394, Mþ; 691,
References
[Ru(PPh3)2Cp]þ; 429, [Ru(PPh3)Cp]þ.
[1] (a) L. Brandsma, H.D. Verkruijsse, Synthesis of Acetylenes, Allenes and
Cumulenes. Elsevier, Amsterdam, 1981, chapter 3, p. 11;
(b) L. Brandsma, Preparative Acetylenic Chemistry. Elsevier, Amsterdam, 1971,
chapter II, p. 15.
[2] (a) C. Hartbaum, G. Roth, H. Fischer, Eur. J. Inorg. Chem. (1998) 191;
(b) C. Hartbaum, H. Fischer, Chem. Ber. 130 (1997) 1063;
(c) C. Hartbaum, G. Roth, H. Fischer, Chem. Ber. 130 (1997) 479.
[3] E. Stander, C. Esterhuysen, J.M. McKenzie, S. Cronje, H.G. Raubenheimer,
Dalton Trans. (2007) 5684.
[4] L. Dahlenburg, A. Weiss, M. Moll, J. Organomet. Chem. 535 (1997) 195.
[5] Y. Kawata, M. Sato, Organometallics 16 (1997) 1093.
[6] (a) R.L. Cordiner, D. Corcoran, D.S. Yufit, A.E. Goeta, J.A.K. Howard, P.J. Low,
Dalton Trans. (2003) 3541;
(b) R.L. Cordiner, M.E. Smith, A.S. Batsanov, D. Albesa-Jové, F. Hartl,
J.A.K. Howard, P.J. Low, Inorg. Chim. Acta 359 (2006) 946.
[7] H. Berke, Chem. Ber. 113 (1980) 1370.
(b) {CuCl(PPh3)}4.
A solution of Ru(C^CC^CH)(PPh3)2Cp 2
(52 mg, 0.07 mmol) in thf (10 ml) was treated with LiBu
(140
m
l, 1.045 M solution in thf) for 30 min at ꢀ78 ꢁC.
{CuCl(PPh3)}4 (25 mg, 0.07 mmol) was then added and the
mixture was allowed to warm to r.t. over 2 h. Solvent was
removed and the residue was dissolved in the minimum
amount of CH2Cl2 and purified by column chromatography
(basic alumina, acetone-hexane 3/7). A yellow fraction con-
tained {Cp(Ph3P)2Ru}C^CC^C{Cu(PPh3)} 19 (30 mg, 40%).
Anal. Calcd (C63H50CuP3Ru): C, 71.04; H, 4.74; M, 1065. Found:
C, 71.08; H, 4.79. IR (CH2Cl2)/cmꢀ1
NMR (C6D6):
4.24 (s, 5H, Cp), 6.89e7.76 (m, 45H, Ph). 31P
NMR:
: n
(C^C) 1994m, 2106m. 1H
d
[8] (a) R.L. Cordiner, A.F. Hill, J. Wagler, Organometallics 27 (2008) 5177;
(b) A.L. Colebatch, R.L. Cordiner, A.F. Hill, K.T.H.D. Nguyen, R. Shang, A.C. Willis,
Organometallics 28 (2009) 4394;
d
50.8 (s, 2P, RuePPh3), 38.5 (s, 1P, CuePPh3). ES-MS
(MeOH)/m/z: 1096, [M þ MeOH]þ; 691, [Ru(PPh3)2Cp]þ; 429,
[Ru(PPh3)Cp]þ.
(c) R.L. Cordiner, P.A. Gugger, A.F. Hill, A.C. Willis, Organometallics 28 (2009)
6632;
(d) A.L. Colebatch, A.F. Hill, R. Shang, A.C. Willis, Organometallics 29 (2010)
6482.
[9] (a) G.M. Jamison, A.E. Bruce, P.S. White, J.L. Templeton, J. Am. Chem. Soc. 113
(1991) 5057;
4.8. Structure determinations
(b) A.E. Enriquez, P.S. White, J.L. Templeton, J. Am. Chem. Soc. 123 (2001)
4992.
Crystallographic data for the structures were collected at 100(2)
K on an Oxford Diffraction Xcalibur diffractometer with mono-
[10] R.L. Cordiner, P.A. Gugger, A.F. Hill, A.C. Willis, Organometallics 30 (2011) 139.
[11] N.A. Ustynyuk, V.N. Vinogradova, D.N. Kravtsov, Yu.F. Oprunenko, V.A. Piven,
Metallo-Org. Khim. 1 (1988) 884.
[12] (a) J.A. Ramsden, W. Weng, A.M. Arif, J.A. Gladysz, J. Am. Chem. Soc. 114
(1992) 5890;
(b) W. Weng, T. Bartik, M. Brady, B. Bartik, J.A. Ramsden, A.M. Arif, J.A. Gladysz,
J. Am. Chem. Soc. 117 (1995) 11922.
[13] J.A. Ramsden, W. Weng, J.A. Gladysz, Organometallics 11 (1992) 3635.
[14] T. Bartik, W. Weng, J.A. Ramsden, S. Szafert, S.B. Falloon, A.M. Arif, J.A. Gladysz,
J. Am. Chem. Soc. 120 (1998) 11071.
[15] L. Dahlenburg, A. Weiss, M. Bock, A. Zahl, J. Organomet. Chem. 541 (1997) 465.
[16] M. Pilar Gamasa, J. Gimeno, I. Godefroy, E. Lastra, B.M. Martín-Vaca, S. García-
Granda, A. Gutiérrez-Rodriguez, J. Chem. Soc., Dalton Trans. (1995) 1901.
[17] (a) M.I. Bruce, M. Ke, P.J. Low, Chem. Commun. (1996) 2405;
(b) M.I. Bruce, M. Ke, P.J. Low, B.W. Skelton, A.H. White, Organometallics 17
(1998) 3539;
(c) M.I. Bruce, B.C. Hall, P.J. Low, M.E. Smith, B.W. Skelton, A.H. White, Inorg.
Chim. Acta 300e302 (2000) 633.
[18] S.N. Semenov, O. Blacque, T. Fox, K. Venkatesan, H. Berke, J. Am. Chem. Soc.
132 (2010) 3115.
[19] (a) R. Dembinski, T. Lis, S. Szafert, C.L. Mayne, T. Bartik, J.A. Gladysz,
J. Organomet. Chem. 578 (1999) 229;
(b) R. Dembinski, T. Bartik, B. Bartik, M. Jaeger, J.A. Gladysz, J. Am. Chem Soc.
122 (2000) 810.
[20] M. Akita, M.-C. Chung, A. Sakurai, S. Sugimoto, M. Terada, M. Tanaka, Y. Moro-
oka, Organometallics 16 (1997) 4882.
[21] A. Wong, P.C.W. Kang, C.D. Tagge, D.R. Leon, Organometallics 9 (1990) 1992.
[22] P. Magnus, D.P. Becker, Chem. Commun. (1985) 640.
[23] (a) M.I. Bruce, A.M. Burgun, C.R. Parker, B.W. Skelton, J. Organomet. Chem. 695
(2010) 619;
(b) M.I. Bruce, N. Scoleri, B.W. Skelton, A.H. White, J. Organomet. Chem. 695
(2010) 1561.
[24] M.I. Bruce, B.G. Ellis, M. Gaudio, C. Lapinte, G. Melino, F. Paul, B.W. Skelton,
M.E. Smith, L. Toupet, A.H. White, Dalton Trans. (2004) 1601.
[25] M. Kira, T. Kadowaki, D. Yin, K. Sakamoto, T. Iwamoto, C. Kabuto, Organo-
metallics 26 (2007) 4890.
ꢀ
chromatic Mo K
merged to N unique (Rint cited) after multiscan absorption correc-
tion (proprietary software), No with I > 2 (I). The structures were
a
radiation,
l
¼ 0.71073 A. Ntot reflections were
s
refined against F2 with full-matrix least-squares using the program
SHELXL-97 [35]. All H-atoms were added at calculated positions
and refined by use of a riding model with isotropic displacement
parameters based on the isotropic displacement parameter of the
parent atom. Anisotropic displacement parameters were employed
throughout for the non-hydrogen atoms. Conventional residuals
R1, wR2 on jF2j are quoted. Neutral atom complex scattering factors
were used.
8 Ru(C^CC^CMe)(dppe)Cp* ^ C41H42P2Ru, M ¼ 697.8. Mono-
clinic, space group P21/n, a ¼ 16.615(2), b ¼ 10.4210(7), c ¼ 21.115
3
(2) A,
2
b
¼ 111.863(9) , V ¼ 3393.0(6) A , Dc ¼ 1.366 g cmꢀ3, Z ¼ 4.
ꢁ
ꢀ
ꢀ
qmax ¼ 64ꢁ,
m
¼ 0.58 mmꢀ1
,
Tmin/max ¼ 0.70/0.89. Crystal 0.40
ꢃ 0.20 ꢃ 0.20 mm. Ntot ¼ 41545, N ¼ 10687 (Rint ¼ 0.035), No ¼ 8049,
R1 ¼0.037, wR2 ¼ 0.100 [I > 2 (I)]; R1 ¼0.049, wR2 ¼ 0.103 (all
s
data).
13 Ru(C^CC^CGePh3)(dppe)Cp* ^ C58H54GeP2Ru, M ¼ 986.6.
Monoclinic, space group P21/n, a ¼ 21.2123(3), b ¼ 9.1713(1),
3
ꢀ
c ¼ 24.8544(4) A,
b
¼ 93.410(1)ꢁ, V ¼ 4826.7(1) A , Dc ¼ 1.358
ꢀ
g cmꢀ3, Z ¼ 4. 2qmax ¼ 68.7ꢁ,
m
¼ 1.04 mmꢀ1, Tmin/max ¼ 0.89. Crystal
0.25 ꢃ 0.10 ꢃ 0.09 mm. Ntot ¼ 177,515, N ¼ 19718 (Rint ¼ 0.101),
No ¼ 8417,
R1 ¼0.043,
wR2 ¼ 0.076
[I > 2s
(I)],
R1 ¼0.113,
wR2 ¼ 0.094 (all data).
Acknowledgements
[26] M.I. Bruce, B.D. Kelly, B.W. Skelton, A.H. White, J. Organomet. Chem. 604
(2000) 150.
[27] M.I. Bruce, B.C. Hall, B.W. Skelton, M.E. Smith, A.H. White, J. Chem. Soc., Dalton
Trans. (2002) 995.
[28] N.C. Payne, R. Ramachandran, R. Puddephatt, Can. J. Chem. 73 (1995) 6.
[29] W. Henderson, J.S. McIndoe, B.K. Nicholson, P.J. Dyson, J. Chem. Soc., Dalton
Trans. (1998) 519.
We thank Professor Brian Nicholson (University of Waikato,
Hamilton, New Zealand) for providing the mass spectra, the ARC for
support of this work and Johnson Matthey plc, Reading, for
a generous loan of RuCl3$nH2O.

3482
M.I. Bruce et al. / Journal of Organometallic Chemistry 696 (2011) 3473e3482
[30] H. Schmidbaur, A. Wohlleben, F. Wagner, O. Orama, G. Huttner, Chem. Ber.
110 (1977) 1748.
[31] D. Evans, J.A. Osborn, G. Wilkinson, Inorg. Synth. 28 (1990) 79.
[32] H.A. Tayim, A. Bouldoukian, F. Awad, J. Inorg. Nucl. Chem. 32 (1970) 3799.
[33] G. Costa, E. Reisenhofer, L. Stefani, J. Inorg. Nucl. Chem. 27 (1965) 2581.
[34] M.I. Bruce, B.K. Nicholson, O. Bin Shawkataly, Inorg. Synth. 26 (1989)
325.
[35] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.