Preparation, structures and some reactions of novel diynyl complexes of iron and ruthenium

Article abstract of DOI:10.1039/b316297b

Reactions between HC≡CC≡CSiMe₃ and several ruthenium halide precursors have given the complexes Ru(C≡CC≡CSiMe ₃)(L₂) Cp′ [Cp′ = Cp, L = CO (1), PPh ₃ (2); Cp′ = Cp*, L₂ = dppe (3)]. Proto-desilylation of 2 and 3 have given unsubstituted buta-1,3-diyn-1-y1 complexes Ru(C≡CC≡CH)(L₂) Cp′ [Cp′ = Cp, L = PPh₃ (5); Cp′ = Cp*, L₂ = dppe (6)]. Replacement of H in 5 or 6 with Au(PR₃) groups was achieved in reactions with AuCl(PR₃) in the presence of KN(SiMe₃) ₂ to give Ru(C≡CC≡CAu(PR₃)}(L ₂)Cp′ [Cp′ = Cp, L = PPh₃, R = Ph (7); Cp′ = Cp*, L₂ = dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped {Cp(Ph₃P)₂Ru} C≡CC≡C{Ru(dppe)Cp*} (10) was obtained from Ru(C≡CC≡CH)(dppe)Cp′ and RuCl(PPh₃)₂Cp. Single-crystal X-ray structural determinations of 1-3 and 6-9 are reported, with a comparative determination of the structure of Fe(C≡CC≡CSiMe ₃)(dppe)Cp′ (4), and those of a fifth polymorph of {Ru(PPh ₃)₂Cp}2(μC≡CC≡C) (12), and {Ru(dppe)Cp}₂(μ-C≡CC≡C) (13).

Full text of DOI:10.1039/b316297b

View Article Online / Journal Homepage / Table of Contents for this issue
Preparation, structures and some reactions of novel diynyl
complexes of iron and ruthenium
Michael I. Bruce,a Benjamin G. Ellis,a,b Maryka Gaudio,a Claude Lapinte,b Giovanni Melino,a
Frédéric Paul,a,b Brian W. Skelton,c Mark E. Smith,a,b Loic Toupetd and Allan H. Whitec
a Department of Chemistry, University of Adelaide, Adelaide, South Australia 5005
b Organométalliques et Catalyse: Chimie et Electrochimie Moléculaire, UMR CNRS 6509,
Institut de Chimie de Rennes, Campus de Beaulieu, 35042 Rennes Cedex, France
c Department of Chemistry, University of Western Australia, Crawley, Western Australia 6009
d Groupe Matière Condensée et Matériaux, UMR CNRS 6626, Université de Rennes 1,
35042 Rennes Cedex, France
Received 12th December 2003, Accepted 23rd March 2004
First published as an Advance Article on the web 19th April 2004
᎐
᎐
᎐
Reactions between HC᎐CC᎐CSiMe and several ruthenium halide precursors have given the complexes
᎐
3
᎐
᎐
Ru(C᎐CC᎐CSiMe )(L )CpЈ [CpЈ = Cp, L = CO (1), PPh (2); CpЈ = Cp*, L = dppe (3)]. Proto-desilylation of 2 and 3
have given unsubstituted buta-1,3-diyn-1-yl complexes Ru(C᎐CC᎐CH)(L )CpЈ [CpЈ = Cp, L = PPh (5); CpЈ = Cp*,
᎐
᎐
3
2
3
2
᎐
᎐
᎐
᎐
2
3
L2 = dppe (6)]. Replacement of H in 5 or 6 with Au(PR3) groups was achieved in reactions with AuCl(PR3) in the
᎐
᎐
presence of KN(SiMe ) to give Ru(C᎐CC᎐CAu(PR )}(L )CpЈ [CpЈ = Cp, L = PPh , R = Ph (7); CpЈ = Cp*, L =
᎐
᎐
3
2
3
2
3
2
᎐
᎐
dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped {Cp(Ph P) Ru}C᎐CC᎐C{Ru(dppe)Cp*} (10) was obtained
from Ru(C᎐CC᎐CH)(dppe)Cp* and RuCl(PPh ) Cp. Single-crystal X-ray structural determinations of 1–3 and 6–9
are reported, with a comparative determination of the structure of Fe(C᎐CC᎐CSiMe )(dppe)Cp* (4), and those of a
fifth polymorph of {Ru(PPh ) Cp} (µ-C᎐CC᎐C) (12), and {Ru(dppe)Cp} (µ-C᎐CC᎐C) (13).
᎐
᎐
3
2
᎐
᎐
᎐
᎐
3
2
᎐
᎐
᎐
᎐
3
᎐
᎐
᎐
᎐
᎐
᎐
᎐
᎐
3
2
2
2
Introduction
The study of diynyl complexes of the Group 8 metals continues
to provide novel chemistry,1,2 while complexes containing C4
chains end-capped by M(PP)CpЈ [M = Fe, Ru, Os; PP = (PPh3)2,
dppe, dppm; CpЈ = Cp, Cp*] have been shown to undergo
a variety of redox processes which suggest that electronic
communication between the two metal centres occurs rather
efficiently by way of the carbon chain.3–9 A variety of pre-
cursors of these complexes has been made, including
compounds containing M–C4R [R = H, SiMe3, Au(PRЈ3)]
fragments. While the syntheses and spectroscopic properties of
several of these have been reported earlier, we have recently
been able to obtain crystalline samples which have been suitable
for successful single-crystal X-ray structural characterisations.
This paper describes and compares several of these structures
and includes previously unreported synthetic procedures and
spectroscopic data.
Results
Syntheses
The chemistry described below is summarised in Scheme 1 and
details follow for the individual syntheses and characterisations.
᎐
᎐
᎐
(a) Ru(C᎐CC᎐CSiMe )(L) CpЈ [CpЈ ؍ Cp, L ؍ CO (1), PPh
᎐
3
2
3
(2); CpЈ ؍ Cp*, L2 ؍ dppe (3)]. The copper()-catalysed coup-
᎐
᎐
ling between RuBr(CO) Cp and HC᎐CC᎐CSiMe in thf/NEt
᎐
᎐
2
3
3
᎐
᎐
᎐
gave Ru(C᎐CC᎐CSiMe )(CO) Cp (1) in good yield. Reactions
between RuCl(PPh ) Cp or RuCl(dppe)Cp* and HC᎐CC᎐
᎐
3
2
᎐
᎐
᎐
᎐
3
2
CSiMe3 in a mixed thf/NEt3 solvent in the presence of Na[BPh4]
᎐
᎐
gave orange–brown Ru(C᎐CC᎐CSiMe )(PPh ) Cp (2) in 94%
Scheme 1
᎐
᎐
3
3 2
᎐
᎐
yield, or bright yellow Ru(C᎐CC᎐CSiMe )(dppe)Cp* (3) in
᎐
᎐
3
79% yield. For 2 and 3, thf was used to dissolve the RuCl-
(PPh3)2Cp or RuCl(dppe)Cp* precursors and heating was
required to facilitate cleavage of the Ru–Cl bond, which is
stronger than the Fe–Cl bond.6c,10 No reaction was observed
after stirring at r.t. for 24 h, but after stirring at 50 ЊC for 16 h
the desired product 2 was obtained in almost quantitative yield.
The IR spectra are characterised by the presence of three
ν(C᎐C) bands between 2181 and 1990 cmϪ1, as found previously
᎐
᎐
᎐
᎐
for Fe(C᎐CC᎐CSiMe )(dppe)Cp* (4), and ascribed to Fermi
᎐
᎐
3
coupling of one of the modes with another oscillator, such as
the SiMe3 group.6c,11 For 1, two ν(CO) bands are observed at
2056 and 2002 cmϪ1. The NMR spectra of 1–3 (Table 1) contain
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4
D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
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Table 1 Spectroscopic data
δH (J(HP)/Hz)
Ϫ1
᎐
Complex [X]
ν(C᎐C)/cm
δP
X
CpЈ
CH2
Ph
᎐
1a [SiMe3]
2 [SiMe3]
3b [SiMe3]
5 [H]
2181m, 2128m, 2114 (sh)
2166m, 2103s, 1997m
2171w, 2095m, 1990w
2107s, 1970 (br)
2109w, 1971w
2116s, 2073m, 1982w
2119m, 2072m, 1981w
2124m, 2073m, 1987m
1966m
–
50.7
81.3
51.0
0.12
0.26
0.23
1.42
1.44
–
–
–
–
–
5.41
4.30
1.53 (1.8)
4.29
1.55
4.28
1.52
1.56
–
–
–
6.92–7.58
6.89–7.86
7.06–7.42
7.09–7.87
7.08–7.59
7.04–7.76
7.08–7.79
6.83–8.16
7.00–8.09
7.03–7.71
1.78, 2.49
–
1.79, 2.54
–
2.15, 2.77
2.19, 2.81
2.18, 3.02
2.03, 2.92
2.01, 2.35
6c [H]
81.3
7 [Au(PPh3)]
8d [Au(PPh3)]
9e [Au{P(tol)3}]
10
11
13
42.5 (PAu), 50.0 (dppe)
42.5 (PAu), 80.8 (dppe)
51.5 (PAu), 82.0 (dppe)
51.4 (PPh3), 86.1 (dppe)
51.5 (PPh3), 82.0 (dppe)
86.7 (dppe)
4.42, 4.77
1.73 (Cp*), 4.32 (Cp)
4.60
1965m
1970m
–
δC (J(CP)/Hz)
Complex [X]
Cα
Cβ
90.84
96.29
115.84
94.34
91.73
–
92.20
92.32
–
–
–
Cγ
Cδ
X
Cp
Ph
1a [SiMe3]
2 [SiMe3]
3b [SiMe3]
5 [H]
92.55
120.67 (24)
120.06
116.51 (24)
124.90 (24)
–
118.65 (23)
118.12 (24)
84.23
94.37
96.59
73.87
75.33
–
94.61
94.57
–
72.74
67.22
66.94
51.54
52.47
0.01
0.93
1.13
–
–
–
–
–
–
87.84
85.59
10.12, 93.40 (2.1)
85.59
10.77, 93.29
87.8
10.26, 93.29
10.16, 93.28
82.06 [Ru(dppe)], 85.57 [Ru(PPh3)2]
10.71, 93.05 (Cp*), 85.94 (Cp)
82.23
–
125.55–138.90
129.16–138.88
125.59–138.63
127.50–138.99
129.4–141.2
127.51–139.13
127.47–142.11
128.17–139.86
127.36–140.02
127.21–143.06
6c [H]
7 [Au(PPh3)]
8d [Au(PPh3)]
9e [Au{P(tol)3}]
10f
–
110.00 (75)
111.40 (128)
–
–
–
–
–
–
11g
–
–
–
–
13h
a δC(CO) 195.50. b δC(CH2) 29.60. c δC(CH2) 29.64. d δC(CH2) 29.79. e δH(Me) 2.40; δC(Me) 21.54, (CH2) 29.71. f δC(CH2) 29.12. g δC(CH2) 30.19.
h δC(CH2) 29.01.
᎐
resonances which are characteristic of the ligand groups
present. For 1, the CO singlet is at δC 195.90. Four resonances in
the 13C NMR spectra of each compound could be assigned to
the carbons of the C4 chain. For 1, Cα–δ are found at δC 92.55,
90.84, 84.23 and 72.74, respectively. For 2 and 3, the presence of
the tertiary phosphine ligands results in a downfield shift, so
that Cα–δ are now observed at δC 120.67 (2) and 120.06 (3), 96.29
and 115.84, 94.37 and 96.59, and 67.22 and 66.94, respectively,
of the ᎐CH proton with the isolobal Au(PR ) (R = Ph, tol)
᎐
3
group could be effected by addition of AuCl(PR3) to solutions
of 5 or 6 in thf, followed by addition of an equivalent of
KN(SiMe3)2 in toluene. The reactions proceeded readily at r.t.
to give Ru{C᎐CC᎐C[Au(PR )]}(PP)CpЈ [PP = (PPh ) , CpЈ =
Cp, R = Ph (7); PP = dppe, CpЈ = Cp*, R = Ph (8), tol (9)]. The
᎐
᎐
᎐
᎐
3
3 2
new ruthenium–gold complexes were characterised spectro-
᎐
scopically, only the IR ν(C᎐C) spectra, consisting of three
᎐
those for Cα showing triplet coupling to the 31P nuclei. The 31
P
bands between 2124 and 1981 cmϪ1, being notable. Altern-
atively, the reaction between 3 and AuCl(PPh3) in methanol,
in the presence of NaOMe, afforded 8 directly in almost
quantitative yield. The solid state structures of 7–9 are
described below.
NMR spectra of 2 and 3 contain singlets at δP 50.7 and 81.3 for
the PPh3 and dppe ligands, respectively. The electrospray mass
spectra of all compounds contained Mϩ ions, in some cases
accompanied by adduct ions formed by addition of MeOH
solvent.
᎐
᎐
᎐
(d) {Cp(Ph P) Ru}C᎐CC᎐C{Ru(dppe)CpЈ} [CpЈ ؍ Cp (10),
᎐
3
2
᎐
᎐
᎐
(b) Ru(C᎐CC᎐CH)(L) CpЈ [CpЈ ؍ Cp, L ؍ PPh (5); CpЈ ؍
Cp* (11)]. With the new butadiynyl–ruthenium complexes
synthesised it was now possible to synthesise new asymmetric
Ru–C4–Ru complexes. Accordingly, the complexes {Cp(Ph3P)2-
᎐
2
3
Cp*, L2 ؍ dppe (6)]. Proto-desilylation of 2 and 3 with [NBu4]F
in wet thf12 gave the versatile precursors Ru(C᎐CC᎐CH)-
᎐
᎐
᎐
᎐
᎐
᎐
᎐
᎐
(PPh ) Cp (5) and Ru(C᎐CC᎐CH)(dppe)Cp* (6) in 74 and 96%
Ru}C᎐CC᎐C{Ru(dppe)CpЈ} [CpЈ = Cp (10), Cp* (11)] were
᎐
᎐
3
2
᎐
᎐
yields, respectively. The former is a mustard-yellow solid, while
made by reaction of 2 with a single equivalent of RuCl-
(dppe)CpЈ in the presence of KF and dbu (Scheme 2).
Alternatively, the reaction between 6 and an equivalent amount
of RuCl(PPh3)2Cp in CH2Cl2/NEt3 in the presence of dbu gave
11 in 35% yield. The yellow products could be crystallised from
6 forms air-stable but moisture-sensitive yellow crystals. In their
᎐
᎐
IR spectra ν(᎐CH) bands at 3298 and 3299, and two ν(C᎐C)
᎐
᎐
bands at 2107 and 1970, or 2109 and 1971 cmϪ1, are also
present. In addition to the resonances for the Ru(L)2CpЈ frag-
ments, the 1H NMR spectra contained singlet resonances
Ϫ1
᎐
CHCl /MeOH. The IR ν(C᎐C) bands are at ca. 1965 cm
,
᎐
3
᎐
for the ᎐CH protons at δ 1.42 and 1.44. The four carbons of
᎐
H
the chain (Cα–δ) resonated at δC 116.51 (5) and 124.90 (6), 94.34
and 91.73, 73.87 and 75.33, and 51.54 and 52.47, respectively,
with Cα giving triplets [both 2J(CP) 24 Hz]. These were assigned
by comparison with similar complexes6–8 and it is notable that
the chemical shifts are not as strongly affected by the different
phosphines as found for 2 and 3. Singlets in the 31P NMR spec-
trum at δP 51.0 or 81.3 were assigned to the tertiary phosphine
ligands.
᎐
᎐
᎐
(c) Ru{C᎐CC᎐CAu(PR )}(L) CpЈ [CpЈ ؍ Cp, L ؍ PPh , R ؍
᎐
3
2
3
Ph (7); CpЈ ؍ Cp*, L2 ؍ dppe, R ؍ Ph (8), tol (9)]. Replacement
Scheme 2
D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
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while the 31P NMR spectra contained two equal intensity
resonances at δP ca. 86 and 51 (for 10) and ca. 82 and ca. 51 ppm
(for 11), assigned to the dppe and PPh3 phosphine ligands,
respectively. The 1H and 13C NMR spectra contained all
expected resonances except for those of the carbon chain,
which were not observed as a result of the poor solubility of the
complexes.
Molecular structures
In the course of this work, the molecular structures of 1–4 and
6–9 were confirmed by single-crystal X-ray structure deter-
minations. Plots of single molecules are shown in Figs. 1–4 and
significant bond parameters are collected in Table 2. Common
features, such as the pseudo-octahedral geometry about the
iron or ruthenium atoms are in accord with a myriad of related
structures to be found in the Cambridge Crystallographic Data
Base.13 For the compounds reported here, Fe–P and average
Fe–C(Cp*) distances are 2.1801, 2.1875(9) and 2.125 Å, with
corresponding Ru–P and Ru–C(Cp*) distances in the ranges
2.286(4)–2.2975(4) (PPh3), 2.256–2.279(1) (dppe) and 2.23(1)–
2.26(2) Å. Angles subtended by the two P atoms [Fe; 84.59(3);
Ru: 81.84–83.93(4)Њ] and by the pair of P, C atoms [Fe: 84.67,
87.70(9)Њ; Ru: 84.01–88.40(4)Њ] are consistent with the pseudo-
octahedral arrangement of ligands and the restricted bite angle
of chelating dppe. Complexes containing the unidentate PPh3
ligand have larger P–Ru–P [99.9, 101.01(2)Њ] and P–Ru–C
[86.62–91.1(4)Њ] angles. Of some interest is a comparison of the
bite angles of the two ligands in the Ru(LL) fragments [LL =
(CO)2, (PPh3)2, dppe]. While this may also be affected by
replacement of Cp in the first two by Cp* in the third, the sums
of angles about the Ru atoms are 268.6 [(CO)2], 274.8 and 279.6
[(PPh3)2], 256.9 [Fe(dppe)] and between 253.1 and 255.8Њ
[Ru(dppe)].
᎐
᎐
Fig. 2 Molecular projections of (a) Ru(C᎐CC᎐CSiMe3)(PPh3)2Cp (2);
᎐
᎐
᎐
᎐
᎐
᎐
(b) Fe(C᎐CC᎐CSiMe3)(dppe)Cp* (4); (c) Ru(C᎐CC᎐CSiMe3)-
᎐
᎐
᎐
᎐
(dppe)Cp* (3).
The focus of interest in the present study is the diynyl ligand.
Complexes 1–4 allow a comparison of changes wrought by
different metals and associated ligands, although it has to be
said that these are not major. The Fe–C [1.875(3) Å] and Ru–C
bonds [1.983(2)–2.015(4) Å] reflect the difference in atomic
radii, as also seen with the M–P distances (above). The diynyl
nature of the carbon chain is shown by the short–long–short
CC bond sequences [1.217–1.231(2), 1.36–1.380(2) and
1.205–1.222(3) Å], which are comparable with those in similar
complexes6–8 and in buta-1,3-diyne itself [1.2176(14), 1.384(2)
Å].14 Of interest here are the differences found for the buta-
᎐
diynyl complex 6, in which the C᎐C bonds are shorter [at 1.186,
᎐
1.193(5) Å] and the central C–C bond longer [at 1.387(5) Å].
Angles at individual carbons C(1–4) are close to linear [range
169.9–179.7Њ], with cumulative bend angles of between 7.2 and
26.4Њ. In these eight complexes, the average angles at C(1–4) are
174.3, 174.8, 178.3, 175.9Њ, respectively, atom C(3) consistently
᎐
᎐
Fig. 1 (a) Molecular projection of Ru(C᎐CC᎐CSiMe3)(CO)2Cp (1)
᎐
᎐
down the Cp(centroid)–R line (molecule 1; molecules 2, 3 are similar).
(b) Unit cell contents, projected down a.
D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
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᎐
᎐
Fig. 3 Molecular projection of Ru(C᎐CC᎐CH)(dppe)Cp* (6).
᎐
᎐
being the least affected by surrounding ligands attached to
the metal centre(s). As can be seen from the plots, the overall
bending results in a displacement of the terminal carbon such
that the M ؒ ؒ ؒ C(4) distances are significantly less than the
respective sums of the interatomic distances.
We have also obtained
a further polymorph of the
᎐
᎐
symmetrical binuclear complex {Ru(PPh ) Cp} (µ-C᎐CC᎐C)
᎐
᎐
3
2
2
(12). On previous occasions15 we have described solid-state
structures of 12 which differ in solvation and in the conform-
ation of the Cp groups (either cis or trans across the C4 chain).
The new modification reported here is the penta-thf solvate
which has the trans conformation. Finally, the molecular
᎐
᎐
structure of {Ru(dppe)Cp} (µ-C᎐CC᎐C) (13), obtained by
᎐
᎐
2
ligand substitution of 12 with dppe in refluxing toluene, con-
firms the expected molecular geometry, with the two Cp rings
being oriented mutually cis. Other structural parameters for the
Ru fragment are similar to those reported for RuCl(dppe)Cp16
and do not merit further comment. Fig. 5 contains plots of 12
and 13. As shown in Table 3, all six structures have virtually
identical bond parameters, although the torsion angles
C(0)–Ru(1) ؒ ؒ ؒ C4 ؒ ؒ ؒ Ru(1Ј)–C(0Ј) [C(0,0Ј) are the centroids
of the Cp rings] vary from Ϫ28.2Њ (cis) to 180Њ (trans).
Separations of the two Ru atoms are 7.795(1) (12) and 7.741(2)
Å (13), some 0.02 and 0.12 Å, respectively, shorter than the
sums of the interatomic distances.
᎐
᎐
Fig. 4 Molecular projections of (a) Ru{C᎐CC᎐CAu(PPh3)}(PPh3)2Cp
᎐
᎐
᎐
᎐
᎐
᎐
(7); (b) Ru{C᎐CC᎐CAu(PPh3)}(dppe)Cp* (8); (c) Ru{C᎐CC᎐CAu-
᎐
᎐
᎐
᎐
[P(tol)3]}(dppe)Cp* (9).
As previously discussed,6c,8c oxidation of M(C᎐CH)(dppe)-
Cp* with [FeCp2][PF6] gives the bis(vinylidenes) [{Cp*-
᎐
᎐
(dppe)M}᎐C᎐CHCH᎐C᎐{M(dppe)Cp*}][PF ] (M = Fe, Ru,
᎐ ᎐ ᎐ ᎐
6 2
Os).6c,8c,9 It is possible that the first oxidation wave in the CV of
both 5 and 6 corresponds to the formation of a similar product.
This agrees with the non-reversibility of both the oxidation
waves. Replacement of H by the isolobal Au(PR3) group
renders the resulting complexes easier to oxidise by between 140
and 290 mV; not surprisingly, use of Au{P(tol)3} in 9 further
facilitates oxidation, E1 being 70 mV below that of 8, but does
not improve the chemical reversibility.
Electrochemistry
We have measured the cyclic voltammograms for most of these
complexes under similar conditions (CH2Cl2, 0.1 V sϪ1, 25 ЊC,
0.1 M [NBu4]PF6) and the observed redox potentials are listed
in Tables 4 and 5. A single irreversible oxidation process at 0.43
V (vs. SCE) is found for 3, which does not become reversible at
higher scan rates. The ruthenium complex 2 also shows a single
irreversible oxidation processes at ϩ0.58 V, whereas the iron
analogue 4 gives one reversible event at ϩ0.00 V. The latter
complex is thermodynamically easier to oxidise by 0.43 V (it
is more electron releasing) than its ruthenium congener. In
contrast, there is no change in the redox potential when SiMe3
in 4 is replaced by H, but there is a significant decrease in the
chemical reversibility of the process (ia/ic = 0.48), suggesting
that the SiMe3 group acts as a protecting group. For 5, an
irreversible one-electron oxidation was observed at ϩ0.52 V,
showing that the butadiynyl complex is easier to oxidise than
the trimethylsilyl-protected derivative by ca. 0.06 V.
Comparison of the (admittedly limited) ranges found for E1
within groups of related complexes is consistent with the ease
of oxidation being
Fe(dppe)Cp* > Ru(dppe)Cp* > Ru(dppe)Cp ≥ Ru(PPh3)2Cp
i.e., consistent with the increase in electron donor power of the
Cp* and dppe ligands over Cp and PPh3. This is also supported
by a comparison of the corresponding chloro complexes
(Table 4), which exhibit a similar trend in their oxidation
potentials.
D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
1604

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Table 2 Selected bond distances (Å) and angles (Њ) for some alkynyl and diynyl ruthenium complexes
Complex
1a,b
2
3
4c
6
Ru–P(1)
Ru–P(2)
Ru–C(cp)
(av.)
Ru–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–Si
1.893, 1.881, 1.887(4)
1.888, 1.885, 1.882(4)
2.235–2.260(3), 2.234–2.252(3), 2.237–2.260(3)
2.243(9); 2.243(10), 2.241(7), 2.246(10)
2.010, 2.015, 2.013(3)
1.216, 1.215, 1.220(4)
1.384, 1.382, 1.373(5)
1.207, 1.213, 1.214(5)
1.841, 1.831, 1.834(4)
2.2980(5)
2.2975(4)
2.225–2.256(2)
2.242(12)
1.988(2)
1.225(2)
1.375(2)
2.2610(3)
2.2775(4)
2.233–2.275(2)
2.258(15)
1.983(2)
1.231(2)
1.371(2)
2.1795(9)
2.1876(9)
2.102–2.142(3)
2.125(17)
1.875(3)
1.226(4)
1.374(4)
2.279(1)
2.256(1)
2.216–2.281(4)
2.250(27)
2.015(4)
1.186(5)
1.387(6)
1.193(6)
1.213(3)
1.824(2)
1.222(3)
1.822(2)
1.220(4)
1.821(3)
P(1)–Ru–P(2)
P(1)–Ru–C(1)
P(2)–Ru–C(1)
Ru–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(3)–C(4)–Si
92.1, 91.1, 91.7(2)
87.9, 88.3, 89.0(1)
90.6, 86.9, 88.2(1)
177.3, 178.3, 177.9(3)
177.8, 178.1, 177.1(4)
178.6, 178.9, 179.1(4)
177.7, 178.1, 179.4(4)
8.6, 6.6, 6.5
101.01(2)
87.15(5)
86.62(5)
179.6(1)
171.1(2)
178.0(2)
174.6(2)
16.7
81.84(1)
85.30(4)
88.40(4)
173.8(1)
176.7(1)
178.9(1)
–
84.61(3)
84.69(9)
87.71(9)
176.0(3)
175.6(3)
179.7(4)
175.2(3)
16.8
83.43(4)
84.2(1)
85.5(1)
173.1(4)
172.7(5)
177.4(5)
Σ(bend) Ru ؒ ؒ ؒ Si
13.5
16.8 [to C(4)]
Complex
7
8
9
12
13
Ru–P(1)
Ru–P(2)
Ru–C(cp)
(av.)
Ru–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–X
2.286(4)
2.297(4)
2.23–2.24(2)
2.236(5)
1.99(1)
1.22(2)
1.36(2)
1.19(2)
1.99(1) [Au]
2.253(4)
2.2616(9)
2.2777(9)
2.220–2.284(3)
2.252(25)
1.992(3)
1.221(5)
1.378(5)
1.205(5)
1.992(3) [Au]
2.2666(8)
2.2571(4)
2.2778(4)
2.230–2.273(2)
2.255(16)
1.995(2)
1.225(2)
1.380(2)
1.211(2)
1.988(2) [Au]
2.2677(5)
2.280(1), 2.291(1)a
2.228(3), 2.246(3)a
2.289(1), 2.285(1)a
2.227–2.238(6), 2.217–2.242(6)a
2.236(7), 2.229(12)a
1.995(5)
2.256(3), 2.258(3)a
2.23–2.25(1), 2.223–2.26(1)a
2.243(9), 2.242(13)a
2.016(7)
1.231(6)
1.377(6)
1.219(6)
1.989(4) [Ru(2)]
–
1.22(1)
1.40(1)
1.22(1)
2.007(8) [Ru(2)]
–
Au–P
P(1)–Ru–P(2)
P(1)–Ru–C(1)
P(2)–Ru–C(1)
Ru–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(3)–C(4)–X
99.9(1)
91.1(4)
88.6(4)
169.9(12)
176(1)
83.62(3)
85.6(1)
86.6(1)
172.2(3)
174.0(4)
179.0(3)
176.5(3) [Au]
177.3(1)
18.3
82.77(1)
84.01(5)
87.50(4)
172.1(1)
175.7(2)
179.6(2)
175.9(2) [Au]
178.32(5)
16.7
103.25(5), 103.10(5)d
86.7(1), 86.3(1)d
82.1(1), 82.5(1)d
175.5(4)
177.3(5)
176.2(6)
82.0(1), 82.3(1)d
85.0(3), 84.3(3)d
81.2(3), 81.5(3)d
177.1(9)
176(1)
172(1)
175(1)
172(1) [Au]
173.7(4)
28.1
174.5(5) [Ru(2)]
–
171.4(9)
–
C(4)–Au–P
Σ (bend) Ru ؒ ؒ ؒ C
a Values for three independent molecules given. b For P(1, 2), read C(110, 120). c For Ru, read Fe; equivalent geometries are given about the Fe atom.
d Values for bonds involving Ru(1, 2) given.
Table 3 Dimensions (Å, Њ) of the Ru–C4–Ru chain in complexes 12 and 13
Complex
Ru(1)–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–Ru(2)
Ru(1) ؒ ؒ ؒ Ru(2)
Torsion angle
Ref.
12
2.01(3)
2.00(1)
2.00(1)
2.001(3)
1.995(4)
2.016(7)
1.24(4)
1.22(1)
1.20(2)
1.218(5)
1.231(6)
1.22(1)
1.32(3)
1.39(1)
1.38(2)
1.369(5)
1.377(6)
1.40(1)
1.24(4)
1.22(1)
1.25(2)
1.218(5)
1.219(6)
1.22(1)
2.01(3)
2.00(1)
2.01(1)
2.001(3)
1.989(4)
2.007(8)
7.768(4)
7.782(1)
7.774(1)
7.805(2)
7.7946(8)
7.741(2)
Ϫ30.6 (cis)
Ϫ32.3 (cis)
Ϫ28.2 (cis)
180 (trans)
Ϫ178.2 (trans)
Ϫ39.4 (cis)
15a
15b
15b
15a
This work
This work
12ؒ0.8MeOH
12ؒ2thf
12ؒ2thf
12ؒ5thf
13
We have described elsewhere the electrochemistry of the
cation between the end-groups is related to the amount of
delocalisation, in the limit the HOMOs extending over the
M–C4–M bridge. While the present range of complexes is
limited, some dependency of KC on the ligands surrounding the
metal centre is found, KC increasing from the lowest value in
13 (Ru/Cp/dppe), through to 10 and 12 (Ru/Cp/PPh3 or dppe),
11 (Ru/Cp/PPh3 ϩ Cp*/dppe) and 14 (Ru/Cp*/dppe) to 15 (the
Fe analogue of 14). The KC values roughly correlate to the
E1 values and are consistent with increased delocalisation
occurring with the better donor ligands.
8
᎐
᎐
binuclear complexes 12 and {Ru(dppe)Cp*} (µ-C᎐CC᎐C) (14).
᎐
᎐
2
The present results with 13 (Table 5) show that replacement
of two PPh3 ligands by dppe has little effect on the various
oxidation potentials of these complexes, values for the mixed
compound 10 lying between the values for 12 and 13. Replace-
ment of Cp by Cp* has a more pronounced effect, with values
for the mixed derivative 11 again lying between those of 12 and
14. The magnitude of the comproportionation constant, KC
(which is the equilibrium constant for reaction (1)),
MLn ϩ [MLn]2ϩ
2[MLn]ϩ
(1)
Discussion
has been used as an indicator of the degree of electron delocal-
isation in the molecule. For complexes 10–15, values for KC are
high, between 1010 and 1012. The extent of electronic communi-
This paper describes the syntheses of several ruthenium com-
plexes containing trimethylsilylbuta-1,3-diynyl groups and the
proto-desilylation of some of them to give synthetically useful
D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
1605

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butadiynyl complexes by reactions which are very similar to
those employed for the analogous iron compounds. Careful
control of the reaction conditions in the syntheses of the diynyl
complexes 1–4, achieved by using Na[BPh4] in a mixed thf/NEt3
solvent, avoids formation of the butatrienylidene and sub-
sequent unwanted reactions. The use of Na[BPh4] or K[PF6] to
facilitate the ionisation of the Cl has much precedent.6 Facile
᎐
replacement of the ᎐CH proton by Au(PR ) (R = Ph, tol) is also
᎐
3
demonstrated. Single-crystal X-ray structure determinations
confirm their characterisation by spectroscopic methods (IR,
NMR, mass).
᎐
Both 2 and 4 show three ν(C᎐C) bands which possibly result
᎐
from the coupling of one of the normal modes with another
oscillator such as the SiMe3 moiety.11 The ν(C᎐C) frequencies
᎐
᎐
decrease when the SiMe3 moiety is replaced by H suggesting an
increase in electron density on the carbon chain.
The C4 chains are essentially linear, although deviations at
individual carbon atoms (range 0.3–10.1Њ; least deviation is
found for Cγ) sum up to between 6.5 and 28.1Њ. This feature is
commonly found in unsaturated Cn chains and can be ascribed
to a low bending force constant or facile distortion within
the crystal lattice as a result of interactions with adjacent
molecules.17 As commented by these authors, no one feature
correlates well with observed distortions of the Cn chain in
molecules of this type.
These complexes are synthetically useful intermediates, sub-
sequent reactions affording a variety of diyndiyl and related
complexes. The present study has extended this range to include
Au(PR3) derivatives. The isolobality of H with Au(PR3) is
reflected in gross similarities between the gold complexes and
the unsubstituted diynyl precursors. Further examples of com-
plexes containing C4 chains end-capped by the same or different
ruthenium-phosphine fragments have also been obtained.
Conclusions
Reliable, high-yield syntheses of several ruthenium complexes
containing diynyl ligands attached to Ru(PP)CpЈ centres have
been developed. Further demonstration of their synthetic
utility is provided by the preparation of gold-containing
᎐
᎐
Fig. 5 Molecular projections of (a) {Ru(PPh3)2Cp}2(µ-C᎐CC᎐C) (12);
᎐
᎐
᎐
᎐
᎐
᎐
(b) {Ru(dppe)Cp}2(µ-C᎐CC᎐C) (13).
derivatives Ru{C᎐CC᎐C[Au(PR )]}(PP)CpЈ and several further
᎐
᎐
᎐
᎐
3
᎐
᎐
examples of complexes {Ru(PR ) CpЈ} (µ-C᎐CC᎐C) [CpЈ = Cp,
᎐
᎐
3
2
2
Cp*; (PR3)2 = (PPh3)2, dppe; not all combinations]. Their
spectroscopic properties are discussed and the structural
characterisation of ten of the complexes is reported. Of interest
is their electrochemical behaviour, which confirm expectations
that the presence of strongly electron donating ligands in
otherwise closely similar complexes results in a decrease in the
oxidation potentials.
Table 4 Electrochemical data for mononuclear complexes
Complex
E1(0/1ϩ)/V
RuCl(PPh3)2Cp
RuCl(dppe)Cp
RuCl(PPh3)2Cp*
RuCl(dppe)Cp*
FeCl(dppe)Cp*
0.595
0.47
0.385
0.28
Ϫ0.22a
0.58b
0.43b
0.00
᎐
᎐
Ru(C᎐CC᎐CSiMe3)(PPh3)2Cp 2
᎐
᎐
Experimental
᎐
᎐
Ru(C᎐CC᎐CSiMe3)(dppe)Cp* 3
᎐
᎐
᎐
᎐
Fe(C᎐CC᎐CSiMe3)(dppe)Cp* 4
᎐
᎐
General experimental conditions
0.52b
0.44b
0.00c
0.38b
0.15b
0.08b
᎐
᎐
Ru(C᎐CC᎐CH)(PPh3)2Cp 5
᎐
᎐
᎐
᎐
All reactions were carried out under dry, high purity argon
using standard Schlenk techniques. Common solvents were
dried, distilled under argon and degassed before use.
Ru(C᎐CC᎐CH)(dppe)Cp* 6
᎐
᎐
᎐
᎐
Fe(C᎐CC᎐CH)(dppe)Cp*
᎐
᎐
᎐
᎐
Ru{C᎐CC᎐CAu(PPh3)})(PPh3)2Cp 7
᎐
᎐
᎐
᎐
Ru{C᎐CC᎐CAu(PPh3)})(dppe)Cp* 8
᎐
᎐
᎐
᎐
Ru{C᎐CC᎐CAu[P(tol)3]})(dppe)Cp* 9
᎐
᎐
Instrumentation
a Ref. 2. b Peak potential for irreversible process. c Partially reversible
(ia/ic = 0.48).
IR spectra were obtained on a Bruker IFS28 FT–IR spectro-
meter. Spectra in CH2Cl2 were obtained using a 0.5 mm
Table 5 Electrochemical data for binuclear complexes
Complex
{Ru(PPh3)2Cp}(µ-C᎐CC᎐C){Ru(dppe)Cp} 10
E1(0/1ϩ)
E2(1ϩ/2ϩ)
∆E1/2
KC(0/1ϩ/2ϩ)
E3(2ϩ/3ϩ)
E4(3ϩ/4ϩ)
6.53 × 1010
2.09 × 1011
6.53 × 1010
9.34 × 109
9.64 × 1010
1.47 × 1012
1.07
1.03
1.03
1.08
1.04
0.95
1.52a
1.56a
1.68a
1.44a
1.51b
–
᎐
᎐
᎐
᎐
Ϫ0.22
Ϫ0.33
Ϫ0.23
Ϫ0.24
Ϫ0.43
Ϫ0.68
0.42
0.34
0.41
0.35
0.22
0.04
0.64
0.67
0.64
0.59
0.65
0.72
᎐
᎐
{Ru(PPh3)2Cp}(µ-C᎐CC᎐C){Ru(dppe)Cp*} 11
᎐
᎐
᎐
᎐
{Ru(PPh3)2Cp}2(µ-C᎐CC᎐C) 12
᎐
᎐
᎐
᎐
{Ru(dppe)2Cp}2(µ-C᎐CC᎐C) 13
᎐
᎐
᎐
᎐
{Ru(dppe)2Cp*}2(µ-C᎐CC᎐C) 14
᎐
᎐
᎐
᎐
{Fe(dppe)2Cp*}2(µ-C᎐CC᎐C) 15
᎐
᎐
a Peak potential for irreversible process. b Partially reversible (ia/ic = 0.7).
D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
1606

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path-length solution cell with NaCl windows. Nujol mull
spectra were obtained from samples mounted between NaCl
discs. NMR spectra were recorded on Bruker AM300WB or
ACP300 (1H at 300.13 MHz, 13C at 75.47 MHz, 31P at 121.503
MHz) instruments. Samples were dissolved in CDCl3, unless
otherwise stated, 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. ES mass spectra: VG Platform 2 or Finnigan LCQ
instruments were used, solutions in MeOH being directly
infused into the instrument. Chemical aids to ionisation were
used as required.18 Cyclic voltammograms were recorded using
a PAR model 263 apparatus, with ferrocene as internal
calibrant ([FeCp2]/[FeCp2]ϩ = ϩ0.46 V). Elemental analyses
were performed at the Centre pour Microanalyses du CNRS,
Vernaison, France, and CMAS, Melbourne, Australia.
the resulting dark red–brown solution stirred at r.t. for 24 h.
The solvent was then removed in vacuo. Washing with cold
MeCN (2 × 10 mL) and Et2O (2 × 10 mL) and drying under
᎐
᎐
oil-pump vacuum gave mustard yellow Ru(C᎐CC᎐CH)-
᎐
᎐
(PPh3)2Cp (5) (670 mg, 74%). Anal. Found: C, 73.11; H, 5.06.
Calc. for C45H36P2Ru: C, 73.06; H, 4.90%. M, 740. IR (Nujol):
Ϫ1
᎐
ν(᎐CH) 3298m cm
.
᎐
᎐
᎐
᎐
(e) Ru(C᎐CC᎐CH)(dppe)Cp* (6). To a solution of 3 (2000
᎐
mg, 2.65 mmol) in thf (30 ml) was added [NBu4]F (0.4 ml of a
1.0 M solution in thf ). The solution was stirred at r.t. for 24 h.
The solution was then evaporated to dryness and a bright
yellow complex could be extracted with hot hexane and filtered
via canula into another Schlenk flask. Extraction was continued
until the hexane extracts were no longer coloured. The yellow
solution was then concentrated to approximately 10 ml giving
a bright yellow crystalline solid that was collected and dried
᎐
᎐
Reagents
on a sintered glass funnel to give Ru(C᎐CC᎐CH)(dppe)Cp (5)
᎐
᎐
(1750 mg, 96%). Anal. Found: C, 69.97; H, 5.63. Calc. for
Na[BPh4] (Aldrich), and [NBu4]F (Aldrich) were used as
received. The compounds RuBr(CO)2Cp,19 RuCl(PPh3)2Cp,20
᎐
C H P Ru: C, 70.26; H, 5.89%; M, 684. IR (Nujol): ν(᎐CH)
᎐
35 40
2
3299 cmϪ1. ES-MS: 684, Mϩ; 635, [Ru(dppe)Cp*]ϩ.
RuCl(dppe)Cp,21 FeCl(dppe)Cp*,22 RuCl(dppe)Cp*,8c {Ru-
23
(PPh3)2Cp}2(µ-C4),8b [FeCp2]PF6 and HC᎐CC᎐CSiMe 24 were
᎐
᎐
᎐
᎐
3
᎐
᎐
᎐
(f ) Ru{C᎐CC᎐C[Au(PPh )]}(PPh ) Cp (7). To a solution of 5
᎐
3
3 2
prepared using the cited methods.
(200 mg, 0.27 mmol) and AuCl(PPh3) (134 mg, 0.27 mmol) in
thf (30 ml) was added K[N(SiMe3)2] (2 ml of 0.5 M solution in
toluene, 1.0 mmol). The mixture was stirred at r.t. for 4 h, after
which time volatiles were removed. The residue was dissolved in
the minimum amount of dichloromethane and the solution was
filtered through cotton wool into stirred hexane (150 ml). The
resulting yellow–brown precipitate was filtered off, washed with
᎐
᎐
᎐
(a) Ru(C᎐CC᎐CSiMe )(CO) Cp (1). CuI (25 mg, 0.13 mmol)
᎐
3
2
was added to a solution of RuBr(CO)2Cp (400 mg, 1.32
mmol) in thf/NEt3 (1/2, 40 ml), followed immediately by
᎐
᎐
HC᎐CC᎐CSiMe (430 mg, 3.50 mmol). The solution was stirred
᎐
᎐
3
in the dark for 45 min, filtered and the solvent was removed.
Column chromatography (basic alumina), eluting with Et2O/
pentane (1/1) gave an orange–yellow band which afforded pale
᎐
᎐
pentane (25 ml) and air dried to give Ru{C᎐CC᎐C[Au(PPh )]}-
᎐
᎐
3
(PPh3)2Cp (7) (300 mg, 93%). Anal. Found: C, 64.01; H,
᎐
᎐
yellow Ru(C᎐CC᎐CSiMe )(CO) Cp (1) (325 mg, 72%) (crystals
᎐
᎐
3
2
4.61. Calc. for C66H56AuP3Ru: C, 63.92; H, 4.55%; M, 1198. IR
from CHCl3/hexane). Anal. Found: C, 50.90; H, 4.02. Calc.
(Nujol): ν(C᎐C) 2116s, 2073m, 1982w cmϪ1. ES-MS: 1920,
᎐
᎐
for C15H14O2RuSiؒCHCl3: C, 51.66; H, 4.01%; M, 344. IR
[M ϩ Au(PPh3)2]ϩ; 1657, [M ϩ Au(PPh3)]ϩ; 1198, Mϩ; 983,
(CH2Cl2): ν(CO) 2056vs, 2002vs cmϪ1 13C NMR: δ 195.50 (s,
.
[Au(PPh3)3]ϩ.
CO). ES-mass spectrum (MS) (MeOH, m/z): 344, Mϩ; 316,
[M Ϫ CO]ϩ.
᎐
᎐
᎐
(g) Ru{C᎐CC᎐C[Au(PPh )]}(dppe)Cp* (8). Method A. A
᎐
3
Schlenk flask was charged with 6 (200 mg, 0.29 mmol) and
AuCl(PPh3) (146 mg, 0.29 mmol) and the solids were dried
under vacuum, after which thf (10 ml) was added followed by
addition of KN(SiMe3)2 (1.16 ml of a 0.5 M solution in toluene,
0.58 mmol). The yellow solution was left to stir at room
temperature for 4 h. The solution was evaporated to dryness on
the rotary evaporator and the solid was extracted in a minimum
of CH2Cl2 and filtered followed by evaporation of the solvent.
To the oily residue was added acetone (5 ml) and crystallisation
began immediately. The flask was left in the freezer for 1 h, and
then the bright yellow crystals were collected and washed with a
᎐
᎐
᎐
(b) Ru(C᎐CC᎐CSiMe )(PPh ) Cp (2).
A Schlenk flask
᎐
3
3 2
was charged with RuCl(PPh3)2Cp (2.0 g, 2.76 mmol), NaBPh4
(1.04 g, 3.00 mmol) and thf/NEt3 (1/1, 60 mL) at r.t. and
HC᎐CC᎐CSiMe (0.70 g, 5.70 mmol) in thf (5 mL) was added.
The orange suspension was then warmed to 50 ЊC and stirred
for 16 h. The solvent was then removed and the residue
extracted with Et2O (3 × 15 mL) and filtered into another
Schlenk tube. The Et2O was then removed and the resulting
orange–brown solid was dried in vacuo to give Ru-
᎐
᎐
᎐
᎐
3
᎐
᎐
(C᎐CC᎐CSiMe )(PPh ) Cp (2) (2.11 g, 94%). Anal. Found:
C, 70.71; H, 5.31. Calc. for C48H44P2RuSi: C, 71.00; H, 5.46%;
᎐
᎐
3
3 2
᎐
᎐
further portion of acetone (5 ml) to give Ru{C᎐CC᎐C[Au-
᎐
᎐
M, 812.
(PPh3)]}(dppe)Cp* (8) (231 mg, 69%). Anal. Found: C, 61.02;
᎐
᎐
᎐
H, 4.71. Calc. for C58H54AuP3Ru: C, 61.00; H, 4.77%; M, 1142.
(c) Ru(C᎐CC᎐CSiMe )(dppe)Cp* (3). To a suspension of
᎐
3
IR (Nujol): ν(C᎐C) 2119m, 2072m, 1981w cmϪ1. ES–MS: 1601,
᎐
RuCl(dppe)Cp* (2000 mg, 2.98 mmol) and Na[BPh4] (1025 mg,
2.98 mmol) in thf/NEt 1/1 (80 ml) was added HC᎐CC᎐CSiMe
᎐
[M ϩ AuPPh3]ϩ; 1142, Mϩ; 721, [Au(PPh3)2]ϩ.
᎐
᎐
᎐
᎐
3
3
Method B. To a solution of NaOMe [from Na (50 mg) in
MeOH (5 ml) was added AuCl(PPh3) (90 mg, 0.18 mmol)
followed directly by 6 (136 mg, 0.18 mmol). The suspension was
stirred for 1 h before being cooled to 0 ЊC in an ice bath. The
bright yellow product was collected, washed with cold MeOH
(2 × 5 ml) and hexane (2 × 10 ml) and dried to give 8 (202 mg,
98%).
(1090 mg, 8.94 mmol). The suspension was allowed to stir at
50 ЊC in a sealed flask for 48 h. The orange suspension was then
evaporated to dryness and a bright yellow complex could
be extracted with hexane and filtered via cannula into another
Schlenk flask. Extraction was continued until the hexane
extracts were no longer coloured. The yellow solution was then
concentrated to approximately 10 ml giving a bright yellow
crystalline solid that was collected and dried on a sintered glass
᎐
᎐
᎐
᎐
᎐
(h) Ru{C᎐CC᎐C[AuP(tol) ]}(dppe)Cp* (9). As for (g),
funnel to give Ru(C᎐CC᎐CSiMe )(dppe)Cp (3) (1600 mg, 79%).
᎐
3
᎐
᎐
3
method A, above, 6 (200 mg, 0.29 mmol) and AuCl{P(tol)3}
(158 mg, 0.29 mmol) in thf (10 ml) were treated with an 0.5 M
solution of KN(SiMe3)2 (1.16 ml of an 0.5 M solution in
toluene, 0.58 mmol). The CH2Cl2 extract was filtered into
Anal. Found: C, 68.12; H, 6.72. Calc. for C35H40P2Ru: C, 68.32;
H, 6.39%; M, 756. ES-MS: 757, [M ϩ H]ϩ; 717, [Cp*-
(dppe)RuC3(OMe)CH2]ϩ; 635, [Ru(dppe)Cp*]ϩ.
᎐
᎐
᎐
᎐
(d) Ru(C᎐CC᎐CH)(PPh ) Cp (5). A Schlenk flask was
rapidly stirred hexane to precipitate Ru{C᎐CC᎐C[AuP(tol) ]}-
᎐
3
᎐
᎐
᎐
3
2
charged with 2 (1.0 g, 1.23 mmol) and thf (40 mL). [NBu4]F
(0.62 mL, 0.62 mmol of a 1.0 M solution in thf ) was added and
(dppe)Cp* (9) as a bright yellow solid (260 mg, 76%). Anal.
Found: C, 61.74; H, 5.04. Calc. for C61H60AuP3Ru: C, 61.88; H,
D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
1607

View Article Online
Table 6 Crystal data and refinement details
Compound
1
2
3
4
6
Formula
M
C14H14O2RuSi
343.20
C53H56P2RuSi
884.14
C43H48P2RuSi
755.96
C43H48FeP2SiؒC7H8
802.83
C40H40P2Ru
683.71
Crystal system
Space group
Triclinic
P1
Monoclinic
P21/c
Monoclinic
P21/n
Triclinic
P1
Monoclinic
P21/c
¯
¯
a/Å
b/Å
c/Å
α/Њ
6.6958(6)
16.119(1)
21.291(2)
82.120(2)
88.887(2)
89.629(2)
2276
11.1851(8)
17.171(1)
24.241(2)
15.6527(8)
13.9997(7)
18.9093(9)
10.4576(6)
14.5424(6)
15.4074(6)
70.850(2)
76.356(2)
78.567(2)
2132
10.344(1)
22.719(2)
14.810(2)
β/Њ
95.572(2)
110.977(1)
109.681(2)
γ/Њ
V/Å3
4634
3869
3277
Z
6
4
4
2
4
Dc/g cmϪ3
µ/mmϪ1
Crystal size/mm
‘T ’min/max
2θmax/Њ
Ntot
1.503
1.10
0.45 × 0.20 × 0.09
0.73
68
34494
17462 (0.030)
13797
0.048
0.056
1.265
0.47
0.25 × 0.12 × 0.07
0.88
1.298
0.55
0.38 × 0.35 × 0.16
0.88
1.250
0.49
0.28 × 0.21 × 0.14
–
54
27563
9770 (n/a)
7484
0.059
0.15
1.379
0.60
0.15 × 0.12 × 0.06
0.83
75
75
68
96657
24383 (0.041)
14615
0.041
80261
20314 (0.040)
14141
0.032
58294
13397 (0.14)
6738
0.054
0.043
N (Rint
No
R
)
Rw
0.035
0.034
Compound
7
8
9
12
13
Formula
M
Crystal system
Space group
a/Å
b/Å
c/Å
C63H50AuP3Ru
1198.05
Monoclinic
P21/c
8.884(6)
31.781(4)
20.480(3)
98.529(2)
5718
C58H54AuP3Ruؒ2CH2Cl2
C61H60AuP3Ruؒ0.125CH2Cl2 C86H70P4Ru2ؒ5C4H8O
C66H58P4Ru2
1177.23
Monoclinic
P21
9.434(2)
18.936(4)
15.324(4)
106.405(4)
2626
1311.89
Monoclinic
P21/n
17.414(2)
17.739(2)
17.806(2)
91.051(3)
5499
1194.73
Monoclinic
P21/n
1790.08
Monoclinic
P21/c
15.673(2)
20.344(3)
22.802(2)
100.819(2)
9247
17.3282(7)
12.8802(5)
23.0007(7)
96.423(1)
5257
β/Њ
V/Å3
Z
4
4
4
4
2
Dc/g cmϪ3
µ/mmϪ1
Crystal size/mm
‘T ’min/max
2θmax/Њ
Ntot
1.391
2.95
0.21 × 0.14 × 0.05
0.79
50
53241
10090 (0.10)
7035
1.584
3.26
0.22 × 0.18 × 0.15
0.87
75
115669
28997 (0.062)
17913
1.509
3.22
0.20 × 0.18 × 0.14
0.82
75
108768
27598 (0.033)
20068
1.286
4.5
0.70 × 0.35 × 0.25
0.69
58
91349
23308 (0.074)
13098
1.489
0.74
0.14 × 0.11 × 0.10
0.63
50
26467
4763 (0.065)
4186
N (Rint
No
)
R
Rw
0.089
0.122
0.041
0.043
0.027
0.027
0.061
0.062
0.048
0.055
᎐
5.11%; M, 1184. IR (Nujol): ν(C᎐C) 2124m, 2073m, 1987w
mmol) in CH2Cl2/NEt3 (2/3, 50 ml) was added via cannula and
the solution was heated at reflux point overnight. The solvent
was removed and the residue was extracted in hot hexane until
no further yellow fractions could be extracted. Removal of
solvent and recrystallisation (acetone) gave {Cp(Ph3P)2Ru}-
᎐
cmϪ1 ES–MS: 1990, [M ϩ Au{P(tol)3}2]ϩ; 1184, Mϩ.
᎐
᎐
᎐
(i) {Cp(Ph P) Ru}C᎐CC᎐C{Ru(dppe)Cp} (10). To a solution
᎐
3
2
containing 2 (200 mg, 0.246 mmol), RuCl(PPh3)2Cp (138 mg,
0.230 mmol) and KF (16 mg, 0.275 mmol) in MeOH (30 ml)
was added dbu (90 mg, 0.59 mmol). The resulting orange–
brown suspension was heated at reflux point for 16 h, after
which time an olive-green precipitate had formed. This was
filtered off, washed with hexane and dried in air. Recrystallis-
᎐
᎐
C᎐CC᎐C{Ru(dppe)Cp*} (11) as an orange solid (68 mg, 35%).
᎐
᎐
᎐
᎐
᎐
(k) {Ru(dppe)Cp} (ꢀ-C᎐CC᎐C) (13). A toluene solution (120
᎐
2
᎐
᎐
ml) containing {Ru(PPh ) Cp} (µ-C᎐CC᎐C) (1.0 g, 0.69 mmol)
᎐
᎐
3
2
2
and dppe (580 mg, 1.46 mmol) was heated at reflux point for
3 d, after which time the colour had deepened to orange–red.
Evaporation of solvent and trituration of the residue with hot
hexane (3 × 25 ml) left bright orange {Ru(dppe)Cp}2-
᎐
᎐
ation (CH Cl /MeOH) gave yellow {Cp(Ph P) Ru}C᎐CC᎐C-
᎐
᎐
2
2
3
2
{Ru(dppe)Cp} (10) (130 mg, 42%). Anal. Found: C, 66.40;
H, 4.53. Calc. for C76H64P4Ru2ؒCH2Cl2: C, 66.33; H, 4.83%;
M, 1303.
᎐
᎐
(µ-C᎐CC᎐C) (13) (705 mg, 86%). Anal. Found: C, 67.29; H,
᎐
᎐
4.94. Calc. for C66H58P4Ru2: C, 67.34; H, 4.97%; M, 1177.
᎐
᎐
᎐
(j) {Cp(Ph P) Ru}C᎐CC᎐C{Ru(dppe)Cp*} (11). Method A.
᎐
3
2
Structure determinations
As in (i) above, 2 (100 mg, 0.123 mmol), RuCl(dppe)Cp*
(83 mg, 0.123 mmol) and KF (9 mg, 0.155 mmol) in MeOH
(15 ml) was treated with dbu (45 mg, 0.30 mmol), to give yellow
Crystal data are provided in Table 6. For all except 4, full
spheres of diffraction data to the indicated limits were
measured at ca. 153 K using a Bruker AXS CCD area-detector
instrument. Ntot reflections were merged to N unique (Rint
quoted) after “empirical”/multiscan absorption correction
(proprietary software), No with F > 4σ(F) being used in the full
matrix least squares refinement. All data were measured using
monochromatic Mo-Kα radiation, λ = 0.71073 Å. Anisotropic
᎐
᎐
{Cp(Ph P) Ru}C᎐CC᎐C{Ru(dppe)Cp*} (11) (76 mg, 45%).
᎐
᎐
3
2
Anal. Found: C, 70.74; H, 5.46. Calc. for C81H74P4Ru2: C, 70.83;
H, 5.43%; M, 1375. ES-MS: 1375, Mϩ; 1112, [M Ϫ Ph]ϩ.
Method B. A Schlenk flask was charged with RuCl(PPh3)2Cp
(106 mg, 0.14 mmol), Na[BPh4] (48 mg, 0.14 mmol) and 6
(100 mg, 0.14 mmol). A degassed solution of dbu (90 mg, 0.59
D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
1608

View Article Online
Y. Zhou and J. A. Gladysz, Organometallics, 1993, 12, 3802;
thermal parameter forms were refined for the non-hydrogen
atoms, (x, y, z, Uiso)H being constrained at estimated values.
Conventional residuals R, Rw on |F| are given [weights: (σ2(F) ϩ
0.0004F 2)Ϫ1]. Neutral atom complex scattering factors were
used; computation used the XTAL 3.7 program system.25
Data acquisition and refinement for 4 were carried out at
Rennes using a Nonius Kappa CCD diffractometer (Mo-Kα
radiation, λ = 0.71069 Å), T = 293 K. The structure was solved
using SHELX97,26 SIR-92 and the MOLEN package.27
Pertinent results are given in the Figures (which show
non-hydrogen atoms with 50% probability amplitude displace-
ment ellipsoids and hydrogen atoms with arbitrary radii of
0.1 Å) and Tables.
(c) M. Brady, W. Weng, Y. Zhou, J. W. Seyler, A. J. Amoroso, A. M.
Arif, M. Böhme, G. Frenking and J. A. Gladysz, J. Am. Chem. Soc.,
1997, 119, 775; (d ) W. E. Meyer, A. J. Amoroso, C. R. Horn,
M. Jaeger and J. A. Gladysz, Organometallics, 2001, 20, 1115.
6 (a) N. Le Narvor, L. Toupet and C. Lapinte, J. Am. Chem. Soc.,
1995, 117, 7129; (b) N. Le Narvor and C. Lapinte, Organometallics,
1995, 14, 634; (c) F. Coat, M.-A. Guillevic, L. Toupet, F. Paul and
C. Lapinte, Organometallics, 1997, 16, 5988; (d ) N. Le Narvor
and C. Lapinte, C.R. Acad. Sci., Paris, Ser. II, 1998, 1, 745;
(e) M. Guillemot, L. Toupet and C. Lapinte, Organometallics, 1998,
17, 1928; ( f ) F. Coat, M. Guillemot, F. Paul and C. Lapinte,
J. Organomet. Chem., 1999, 578, 76; (g) H. Jiao, K. Costuas,
J. A. Gladysz, J.-F. Halet, M. Guillemot, L. Toupet, F. Paul and
C. Lapinte, J. Am. Chem. Soc., 2003, 125, 9511.
7 (a) M. Akita, M.-C. Chung, A. Sakurai, S. Sugimoto, M. Terada,
M. Tanaka and Y. Moro-oka, Organometallics, 1997, 16, 4882.
8 (a) M. I. Bruce, L. I. Denisovich, P. J. Low, S. M. Peregudova and
N. A. Ustynyuk, Mendeleev Commun., 1996, 200; (b) M. I. Bruce,
P. J. Low, K. Costuas, J.-F. Halet, S. P. Best and G. A. Heath, J. Am.
Chem. Soc., 2000, 122, 1949; (c) M. I. Bruce, B. G. Ellis, P. J. Low,
B. W. Skelton and A. H. White, Organometallics, 2003, 22, 3184.
9 M. I. Bruce, K. A. Kramarczuk, B. W. Skelton, A. H. White,
unpublished results.
10 See, for example: D. M. P. Mingos, Essential Trends in Inorganic
Chemistry, Oxford Univ. Press, Oxford, 1998, p. 361.
11 (a) F. Coat, P. Thominot and C. Lapinte, J. Organomet. Chem., 2001,
629, 39; (b) F. Paul, J.-Y. Mevellec and C. Lapinte, Dalton Trans.,
2002, 1783.
12 T. B. Peters, J. C. Bohling, A. M. Arif and J. A. Gladysz,
Organometallics, 1999, 18, 3261.
13 Cambridge Crystallographic Data Centre, ConQuest 1.5, November
2002.
14 M. Tanimoto, K. Kuchitsu and Y. Morino, Bull. Chem. Soc. Jpn.,
1971, 44, 386.
15 (a) M. I. Bruce, P. Hinterding, E. R. T. Tiekink, B. W. Skelton and
A. H. White, J. Organomet. Chem., 1993, 450, 209; (b) M. I. Bruce,
B. C. Hall, B. D. Kelly, P. J. Low, B. W. Skelton and A. H. White,
J. Chem. Soc., Dalton Trans., 1999, 3719.
CCDC reference numbers 223445–223453 (1–3, 6–9, 12, 13)
and 224446 (4).
See http://www.rsc.org/suppdata/dt/b3/b316297b/ for crystal-
lographic data in CIF or other electronic format.
Variata
2, 3: (x, y, z, Uiso)H were refined (solvent excepted).
4: The toluene solvent molecule was modelled as disordered
over two sites, occupancies set at 0.7 and complement after trial
refinement. Some difficulties with the refinement have resulted
in a larger than usual (shift/error)max
.
7: Weak and limited data would support anisotropic
displacement parameter form refinement for Ru, Au, P only.
8: The CH2Cl2 solvent molecules were each modelled as
disordered in concert over two sets of sites, occupancies refining
to 0.611(1) and complement.
9: The CH2Cl2 solvent molecule was modelled as disordered,
site occupancy set at 0.25 after trial refinement.
12: The thf solvent molecules were refined with constrained
geometries; T = 300 K.
16 (a) S. Suravajjala and L. C. Porter, Acta Crystallogr., Sect. C, 1993,
49, 1456; (b) W. H. Pearson, J. E. Shade, J. E. Brown and
T. E. Bitterwolf, Acta Crystallogr., Sect. C, 1996, 52, 1106.
17 (a) S. Szafert and J. A. Gladysz, Chem. Rev., 2003, 103, 4175;
(b) W. Mohr, J. Stahl, F. Hampel and J. A. Gladysz, Inorg. Chem.,
2001, 40, 3263; (c) R. Dembinski, T. Lis, S. Szafert, C. L. Mayne,
T. Bartik and J. A. Gladysz, J. Organomet. Chem., 1999, 578, 229.
18 W. Henderson, J. S. McIndoe, B. K. Nicholson and P. J. Dyson,
J. Chem. Soc., Dalton Trans., 1998, 519.
19 (a) D. H. Gibson, W.-L. Hsu, A. L. Steinmetz and B. V. Johnson,
J. Organomet. Chem., 1981, 208, 89; (b) R. J. Haines and
A. L. du Preez, J. Chem. Soc., Dalton Trans., 1972, 944.
20 M. I. Bruce, C. Hameister, A. G. Swincer and R. C. Wallis, Inorg.
Synth., 1990, 28, 270.
13: Friedel data were initially retained distinct, xabs refining to
a value not significantly different from 0.5, whereupon they
were merged.
Acknowledgements
We thank the Australian Research Council for support and,
with CNRS, France, for exchange awards which made this
work possible. We are grateful to Professor B. K. Nicholson
(University of Waikato, Hamilton, New Zealand), for
obtaining the mass spectra for us. Johnson Matthey plc,
Reading, UK, is thanked for a generous loan of RuCl3ؒnH2O.
21 A. G. Alonso and L. B. Reventos, J. Organomet. Chem., 1998, 338,
249.
22 C. Roger, P. Hamon, L. Toupet, H. Rabaa, J.-Y. Saillard,
J.-R. Hamon and C. Lapinte, Organometallics, 1991, 10, 1045.
23 N. G. Connelly and W. E. Geiger, Chem. Rev., 1996, 96, 877.
24 B. Bartik, R. Dembinski, T. Bartik, A. M. Arif and J. A. Gladysz,
New J. Chem., 1997, 21, 739.
25 The XTAL 3.7 System, ed. S. R. Hall, D. J. du Boulay and
R. Olthof-Hazekamp, University of Western Australia, Perth,
2000.
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D a l t o n T r a n s . , 2 0 0 4 , 1 6 0 1 – 1 6 0 9
1609