Some alkynyl-ruthenium complexes containing di-imine and tertiary phosphine ligands

Article abstract of DOI:10.1002/zaac.200800020

Reactions between [RuCl₂(PPh₃)₂(Bu ₂^tbpy)], (1), and terminal alkynes in the presence of Tl[PF₆], followed by chromatography on alumina, have given the mono-alkynyl complexes [RuCl(C≡CR)(PP

Full text of DOI:10.1002/zaac.200800020

DOI: 10.1002/zaac.200800020
Some Alkynyl-Ruthenium Complexes Containing Di-Imine and Tertiary
Phosphine Ligands
Michael I. Brucea,*, Benjamin C. Halla, Brian W. Skeltonb, and Allan H. Whiteb
a Adelaide 5005/South Australia, University of Adelaide, School of Chemistry and Physics
b Crawley 6009/Western Australia, School of Biomedical, Biomolecular and Chemical Sciences, Chemistry M313, The University of
Western Australia
Received January 19th, 2008.
Abstract. Reactions between [RuCl2(PPh3)2(Bu2t bpy)], (1), and
terminal alkynes in the presence of Tl[PF6], followed by chromatog-
raphy on alumina, have given the mono-alkynyl complexes
[RuCl(CϵCR)(PPh3)2(Bu2t bpy)] (R
CO2Me 4, Fc 5, CPh2(OH) 6), of which the single-crystal XRD
molecular structures of 3, 4 and 5 are reported.
ϭ
Ph 2, C6H4NO2Ϫ4 3,
Keywords: Alkynyl; Ruthenium; Crystal structure; Phosphine
ligand
Introduction
Extensive studies of platinum(II) complexes containing
alkynyl and nitrogen ligands such as 2,2Ј-bipyridyl and
2,6:6Ј,2Љ-terpyridyl have shown that they possess interesting
photoluminescence properties [1Ϫ6]. Theoretical investi-
gations reveal that the HOMO is metal-based and that the
LUMO is centred on the diimine ligand. Similar results
have also been reported for rhenium complexes contain-
ing CO and diimine ligands [7Ϫ9]. More recently, the
ligand arrangement in compounds of the type
[Ru(CϵCR)2(bpy)(PRЈ3)2] has been suggested to resemble
the photo-active centres in the platinum(II) complexes, with
a series of compounds [RuCl(CϵCR)(Me2bpy)(PPh3)2] be-
ing prepared and structurally characterized [10]. The latter
work coincided with similar studies carried out by us using
the But2bpy ligand, our conclusions being similar to those
described in that reference. The present paper reports the
syntheses of five related complexes 2-6, derivative of
[RuCl2(But2bpy)(PPh3)2] (1), and the molecular structures of
three of them (3-5), together with the results of some elec-
trochemical studies.
ence of Tl[PF6] at ambient temperatures. Work-up involved
the removal of solvent under reduced pressure, followed by
chromatography of an extract of the residue in the
same solvent on a column of alumina. By this method,
the complexes [RuCl(CϵCR)(But2bpy)(PPh3)2] (R ϭ Ph 2,
C6H4NO2Ϫ4 3, CO2Me 4, Fc 5, CPh2(OH) 6) were ob-
tained and characterised by elemental microanalyses and
the usual spectroscopic methods. The structures of the
methyl propiolate and ethynylferrocene complexes were also
confirmed by single-crystal X-ray diffraction studies.
The complex with R ϭ But defined in ref. [10], is denoted
compound 7 for ease in comparison.
Results and Discussion
Reactions of [RuCl2(But2bpy)(PPh3)2] (1) [11] and 1-alkynes
were carried out in dichloromethane solution in the pres-
The Nujol IR spectra contained ν(CϵC) bands between
2066 and 2020 cmϪ1, while the ester group in 4 gave ν(CO)
bands at 1915 and 1650 cmϪ1; compound 6 has ν(OH) at
1
3400 cmϪ1. In the H NMR spectra, sharp resonances for
the But protons are found in the range δ 1.20-1.43 for all
complexes, with CO2Me in 4 at δ 2.84, ferrocenyl protons
in 5 at δ 4.04 (C5H4) and 3.57 (Cp) and a broad signal for
the OH group in 6 at δ 1.86. Resonances in the 13C NMR
group were found between δ 30.4-30.6 (CMe3) 34.51-35.2
* Prof. Dr. Michael I. Bruce
School of Chemistry and Physics, University of Adelaide
Adelaide 5005 South Australia
Tel: ϩ (618) 8303 5939
Fax: ϩ (618) 8303 4358
email: michael.bruce@adelaide.edu.au
Z. Anorg. Allg. Chem. 2008, 634, 1097Ϫ1101
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1097

M. I. Bruce, B. C. Hall, B. W. Skelton, A. H. White
Fig. 1 Projection of a single molecule of 5.
(CMe3) (5 was an exception, with signals at δ 25.21 and
29.03, respectively), and CϵC at δ 82-89 and 109.4-115.6.
For 4, the CO2Me group gave signals at δ 48.5 and 154.2,
and for 5, the Fc carbon atoms were at δ 67.2 (Cp) and
66.8 (C5H4). The 31P NMR spectrum of 6 contained a res-
onance at δ 23.7 for the PPh3 ligand. The ES-MS [12] con-
tained molecular ions which generally fragmented by loss
of Cl, CϵCR and PPh3 groups. Aggregate ions [M ϩ Na]ϩ
were found for 3, 4 and 5 when NaOMe was added to the
MeOH solvent.
with angles at C(1) and C(2) being 176.1(2), 176.3(3) (3),
176.1(7), 174.0(7) (4) and 169.9(8), 173.4(9)° (5).
The phenylethynyl complex 2 shows single-electron pro-
cesses at E ϭ ϩ0.15 and ϩ0.36 V, the latter also being
found for 3 at E ϭ ϩ0.35 V. These correspond to oxidation
from RuII to RuIII, the HOMO having been shown to be
metal-based [10]. The presence of the strongly electron-
withdrawing ester group in 5 increases the potentials to
E ϭ ϩ0.47 and ϩ0.88 V, while the ferrocenyl analogue is
oxidized at E ϭ ϩ0.07 and ϩ0.67 V, as expected for the
electron-donating metallocene.
The results of the X-ray studies of 3, 4 and 5 confirm
the overall molecular structures with mutually trans PPh3
ligands and chelating But2bpy ligands on an octahedral
ruthenium atom. The two nitrogen atoms of the chelating
bpy group and the chlorine and Ru-alkynyl carbon atoms
are coplanar, with bond parameters closely resembling
those of the Me2bpy analogues of ref. [10]. As found earlier,
the Ru-N distances differ, being shorter for the bond
Experimental Section
General Considerations
All reactions were carried out under dry nitrogen, although nor-
mally no special precautions to exclude air were taken during
subsequent work-up. Common solvents were dried, distilled under
argon and degassed before use. Separations were carried out by
preparative thin-layer chromatography on glass plates (20 x 20 cm2)
coated with silica gel (Merck, 0.5 mm thick).
˚
trans to Cl (2.030(6)Ϫ2.050(6) A) than for that trans
˚
to
C(1)
(2.095(6)Ϫ2.110(6) A)
respectively.
In
[RuCl2(But2bpy)(PPh3)2] (1) (in which C(1) is replaced by a
second chlorine atom), by contrast, the Ru-N distances are
˚
similar, being 2.040, 2.046(2) A [11]; Ru-Cl are 2.4470(8),
˚
Instruments
2.4567(8) A, the hydrogen-bond from the latter to a lattice
H2CCl2 having little impact. Of interest are the Ru-C(1) dis-
tances [2.045(2) (3) (mol. 2; values for mol. 1 concerning
C(1) are clearly aberrant, presumably in consequence of the
widespread disorder in the structure (see below)), 1.987(8),
2.005(4) (4), 2.023(2) A (5)], clearly single bonds, and the
departures from linearity along the Ru-C(1)-C(2) sequence,
Nujol IR spectra were obtained on a Bruker IFS28 FT-IR spec-
trometer from samples mounted between NaCl discs. NMR spectra
were recorded on a Varian 2000 instrument (1H at 300.13 MHz,
13C at 75.47 MHz, 31P at 121.50 MHz). Samples were dissolved in
CDCl3 contained in 5 mm sample tubes. Chemical shifts are given
˚
1
in ppm relative to internal tetramethylsilane for H and 13C NMR
1098
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© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 1097Ϫ1101

Some Alkynyl-Ruthenium Complexes
Table 1 Selected ruthenium atom environment descriptors
Atoms
3 (mols. 1,2)
4 (mols. 1,2)a)
5
7 [10]b)
1c)
˚
Distances/A
Ru-P(1)
Ru-P(2)
Ru-N(11)
Ru-N(21)
Ru-C(1)
Ru-Cl
2.3596(4), 2.3618(5)
(2.3596(4), 2.3618(5))
2.042(2), 2.038(1)
2.107(1), 2.108(2)
2.084(2), 2.045(2)
2.4305(6), 2.4390(5)
0.968(2), 1.117(3)
1.584(3), 1.476(3)
2.366(2), 2.365(2)
2.356(2), 2.358(2)
2.040(6), 2.050(6)
2.095(6), 2.124(6)
1.987(8), 2.005(8)
2.443(2), 2.442(2)
1.19(1), 1.17(3)
2.350(2)
2.339(2)
2.030(6)
2.110(6)
2.023(8)
2.424(2)
1.137(11)
1.471(12)
2.370(1)
2.347(1)
2.051(3)
2.120(4)
2.053(5)
2.464(1)
1.174(6)
1.491(8)
2.3744(9)
2.3730(8)
2.040(2)
2.046(2)
2.4470(8)
2.4567(8)
Ϫ
C(1)-C(2)
C(2)-X
1.43(1), 1.45(1)
Ϫ
Angles/°
P(1)-Ru-P(2)
P(1)-Ru-N(11)
P(1)-Ru-N(21)
P(1)-Ru-C(1)
P(1)-Ru-Cl
174.62(2), 174.95(2)
90.569(10), 90.479(9)
92.691(8), 92.526(10)
87.333(8), 87.488(11)
89.848(10), 89.914(9)
(90.569(10), 90.478(9))
(92.691(8), 92.526(10))
(87.333(8), 87.488(11))
(89.848(10), 89.915(9))
77.97(6), 77.42(6)
174.15(7), 174.15(8)
90.8(2), 91.6(2)
93.5(2), 91.4(2)
85.8(2), 88.6(2)
88.97(6), 88.69(7)
92.9(1), 91.7(2)
91.6(2), 94.0(2)
89.5(2), 86.4(2)
88.12(6), 88.83(8)
78.3(2), 77.7(2)
94.0(3), 93.4(3)
169.8(2), 170.5(2)
172.3(3), 171.1(3)
91.5(2), 92.8(2)
96.1(2), 96.1(2)
176.1(7), 175.5(7)
169.9(8), 173.9(11)
173.74(7)
91.6(2)
92.5(2)
90.9(2)
88.39(7)
92.0(2)
93.3(2)
83.7(2)
89.04(7)
77.7(2)
94.0(3)
169.5(2)
171.0(3)
91.8(2)
96.5(2)
174.0(7)
173.4(9)
172.02(4)
88.8(1)
94.3(1)
86.1(1)
90.04(4)
96.1(1)
92.8(1)
87.5(2)
86.25(4)
78.4(1)
92.8(1)
169.18(9)
171.2(2)
90.94(9)
97.9(1)
173.6(4)
176.1(6)
177.47(3)
91.43(7)
91.63(7)
88.82(3)
89.90(3)
90.72(7)
90.09(7)
89.75(3)
88.12(3)
79.32(10)
92.32(7)
173.26(7)
171.63(7)
94.04(7)
94.32(3)
Ϫ
P(2)-Ru-N(11)
P(2)-Ru-N(21)
P(2)-Ru-C(1)
P(2)-Ru-Cl
N(11)-Ru-N(21)
N(11)-Ru-C(1)
N(11)-Ru-Cl
N(21)-Ru-C(1)
N(21)-Ru-Cl
C(1)-Ru-Cl
94.52(6), 94.82(7)
171.02(4), 171.02(5)
172.49(7), 172.25(6)
93.05(5), 93.60(4)
94.45(5), 94.16(5)
179.6(2), 176.1(2)
Ru-C(1)-C(2)
C(1)-C(2)-X
174.3(2), 176.3(2)
Ϫ
a) In 4, C(3)-O(3,4) (mols. 1,2) are 1.205(14), 1.224(11); 1.354(14), 1.349 (12); C(2)-C(3)-O(3,4) are 128.7(10), 126.6(9); 111.5(9), 112.9(8)°.
b) Ref. [10]; T was 173 K.
c) For the alkynyl pendant, read Cl(1) [11] (the persistent chlorine atom being Cl(2)).
Table 2 Crystal Data and Refinement Details
Complex
3
4
5
Formula
C62H58ClN3O2P2Ru
1075.6
monoclinic
P2/m (# 11)
19.3658(5)
16.1648(5)
20.6410(5)
C58H57ClN2O2P2Ru
1012.6
C66H63ClFeN2P2Ru
1138.6
monoclinic
P21/n (# 14)
16.470(2)
17.166(2)
19.612(3)
MW/Dalton
Crystal system
Space group
triclinic
¯
P1 (# 2)
˚
a/A
12.487(1)
19.737(2)
21.644(1)
94.709(7)
90.233(6)
101.339(8)
5211
˚
b/A
˚
c/A
α/deg.
β/deg.
γ/deg.
112.298(3)
91.200(10)
3
˚
V/A
5978
1.195
5544
1.364
ρc/g cmϪ3
1.291
Z
4
55
0.40
0.86
4
52
0.46
0.79
4
50
0.68
0.92
2θmax/deg.
μ(Mo-Kα)/mmϪ1
Tmin/max
Crystal dimensions/mm
Ntot
0.23 ϫ 0.16 ϫ 0.11
46055
10906 (0.063)
4712
0.35 ϫ 0.17 ϫ 0.16
72411
20160 (0.055)
14261
0.22 ϫ 0.22 ϫ 0.12
66486
9445 (0.059)
5305
N (Rint
No
)
R
0.051 (R1)
0.108 (wR2) (0.057)
0.086
0.163 (50)
0.072
0.082 (0.004)
Rw (nw/a)
spectra and external H3PO4 for 31P NMR spectra. Electrospray
mass spectra (ES MS) were obtained from samples dissolved in
MeOH containing some NaOMe to aid ionisation [12]. Solutions
were injected into a Varian Platform II spectrometer via a 10 ml
injection loop. Nitrogen was used as the drying and nebulising gas.
Electrochemical samples (1 mM) were dissolved in CH2Cl2 contain-
ing 0.5 M [NBu4](BF4) as the supporting electrolyte for the spectro-
electrochemical experiments. Cyclic voltammograms were recorded
using a PAR model 263 potentiometer, with a saturated calomel
electrode. A 1 mm path-length cell was used with a Pt-mesh
working electrode, Pt wire counter and pseudo-reference electrodes.
Ferrocene was used as internal calibrant [FeCp2]/[FeCp2]ϩ
ϭ
0.46 V). Elemental analyses were by CMAS, Belmont, Vic., Aus-
tralia.
Z. Anorg. Allg. Chem. 2008, 1097Ϫ1101
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1099

M. I. Bruce, B. C. Hall, B. W. Skelton, A. H. White
876, [MϪPPh3]ϩ; 841, [MϪClϪPPh3]ϩ; 795, [MϪClϪPPh3Ϫ3Me]ϩ. Elec-
trochemistry (CH2Cl2): E1 ϭ 0.068, E2 ϭ 0.670 V.
Reagents
[RuCl2(Bu2t bpy)(PPh3)2] was obtained by the cited method [11].
Other reagents were commercial products and were used as re-
ceived.
[RuCl{CϵCCPh2(OH)}(PPh3)2(Bu2t bipy)] (6).
A solution of 1
(100 mg, 0.10 mmol) and HCϵCCPh2OH (31 mg, 0.15 mmol) in
CH2Cl2 (15 ml) with TlPF6 (36 mg, 0.10 mmol) was stirred at r.t.
for 6 h. Solvent was removed and a CH2Cl2 extract of the residue
was filtered through cotton wool into cold hexane (50 ml) to give
red-purple [RuCl{CϵCCPh2(OH)}(PPh3)2(Bu2t bipy)] (6) (98 mg,
86 %). A satisfactory elemental analysis was not obtained for this
complex.
[RuCl(CϵCPh)(PPh3)2(Bu2t bpy)] (2). To a solution of 1 (200 mg,
0.21 mmol) and HCϵCPh (31 μl, 0.30 mmol) in CH2Cl2 (15 ml)
was added Tl[PF6] (72 mg, 0.21 mmol) and the resulting solution
was stirred at r.t. for 3 d. The solvent was removed and the residue
extracted with CH2Cl2 and purified on an alumina column. Elution
with acetone/hexane (3:7) gave a red fraction, which was recrys-
tallized from CH2Cl2/hexane to give red microcrystalline
[RuCl(CϵCPh) (PPh3)2(Bu2t bpy)] (2) (121 mg, 57 %). Anal. Calcd
for C62H59ClN2P2Ru (M ϭ 1030): C, 72.25; H, 5.77; N, 2.72;
Found: C, 72.13; H, 5.80; N, 2.68 %.
IR (nujol, cmϪ1): ν(CϵC) 2056. 1H NMR (CDCl3): δ 1.25 (s, 18H, But),
6.37, 8.49 (2 x d, 2H, Hbpy), 6.98Ϫ7.72 (m, 37H, ArH). 13C NMR (CDCl3):
δ 30.61 (s, CMe3), 34.51 (s, CMe3), 89.15 (s, CϵC), 115.62 (s, CϵC), 127.13,
128.02, 128.29, 128.76, 132.14, 134.17 (s, ArH) ppm. ES-MS (MeOH, m/z):
1030, Mϩ; 995, [MϪCl]ϩ; 893, [MϪClϪCϵCPh]ϩ; 733, [MϪClϪPPh3]ϩ.
Electrochemistry (CH2Cl2): E1 ϭ 0.15 V, E2 ϭ 0.36 V.
IR (nujol, cmϪ1): ν(OH) 3400, ν(CϵC) 2059. 1H NMR (CDCl3): δ 1.28 (s,
18H, But), 1.86 (br s, 1H, OH), 6.83, 8.21 (2 x d, 2 x 2H, Hbpy), 6.99Ϫ7.72
(m, 42H, ArH). 13C NMR (CDCl3): δ 30.43 (s, CMe3), 127.07, 127.93, 134.12
(s, ArH) ppm. 31P NMR (CDCl3): δ 23.69 (s, PPh3). ES-MS (MeCN/Na-
OMe, m/z): 1119, [MϪOH]ϩ; 897, [MϪPPh3
ϩ
Na]ϩ; 857,
[MϪPPh3ϪOH]ϩ; 821, [MϪPPh3ϪClϪOH]ϩ; 748, [MϪPPh3ϪPh2OH ϩ
MeCN]ϩ;
708,
[MϪPPh3ϪCϵCCPh2OH
ϩ
MeCN]ϩ;
667,
[MϪPPh3ϪCϵCCPh2OH]ϩ, 631, [MϪPPh3ϪClϪCϵCCPh2OH]ϩ.
Structure determinations
Full spheres of diffraction data were measured at ca. 100 K using
an Oxford Diffraction CCD area-detector instrument. Ntot reflec-
tions were merged to N unique (Rint cited) after ’empirical’/multi-
scan absorption correction (proprietary software), No with F >
4σ(F) being considered ’observed’. All data were measured using
monochromatic Mo-Kα radiation, λ ϭ 0.71073 A. Anisotropic dis-
placement parameter forms were refined for the non-hydrogen
atoms, (x, y, z, Uiso)H being included following a riding model, in
[RuCl(CϵCC6H4NO2)(PPh3)2(Bu2t bpy)] (3). Similarly, 1 (200 mg,
0.21 mmol) and HCϵCC6H4NO2 (31 mg, 0.21 mmol) in CH2Cl2
(15 ml) with Tl[PF6] (72 mg, 0.21 mmol) gave a purple fraction,
which was recrystallized from CH2Cl2/hexane to give purple micro-
crystalline [RuCl(CϵCC6H4NO2)(PPh3)2(Bu2t bpy)] (3) (135 mg,
60 %). Anal. Calcd (C62H58ClN3O2P2Ru): C, 69.23; H, 5.44; N,
3.91; M, 1075; Found: C, 69.30; H, 5.47; N, 4.02 %.
˚
the full matrix least squares refinements on F2. Neutral atom com-
plex scattering factors were used; computation used the XTAL 3.7
[weights: (σ2(F2) ϩ nwF2)Ϫ1] and SHELXL 97 [weights: (σ2(F2) ϩ
(aP)2)Ϫ1 (P ϭ (F2o ϩ 2F2c)/3] program systems [13]. Pertinent results
are given in the Figure (which shows the non-disordered 5 as
exemplary, non-hydrogen atoms having 50 % probability amplitude
displacement envelopes and hydrogen atoms with arbitrary radii of
IR (nujol, cmϪ1): ν(CϵC) 2034. 1H NMR (CDCl3): δ 1.28, 1.36 (s, 18H,
But), 6.20, 8.09, 8.81 (3 x d, 3 x 2H, Hbpy), 6.84Ϫ7.76 (m, 34H, ArH). 13C
NMR (CDCl3): δ 30.60 (s, CMe3), 34.81 (s, CMe3), 82.27 (s, CϵC), 110.71
(s, CϵC), 123.07Ϫ134.16 (m, ArH) ppm. ES-MS (MeOH/NaOMe, m/z):
1098, [M
[MϪCϵCC6H4NO2
[MϪClϪPPh3 ϩ Na]ϩ. Electrochemistry (CH2Cl2): E1 ϭ 0.35 V.
ϩ
Na]ϩ; 1063, [MϪCl
ϩ
Na]ϩ; 1040, [MϪCl]ϩ; 952,
ϩ
Na]ϩ; 894, [MϪCϵCC6H4NO2
Ϫ
Cl]ϩ; 801,
[RuCl(CϵCCO2Me)(PPh3)2(Bu2t bpy)] (4). Similarly,
1
(200 mg,
˚
0.1 A), and in the Tables.
0.21 mmol) and HCϵCCO2Me (25 mg, 0.30 mmol) in CH2Cl2
(15 ml) with Tl[PF6] (72 mg, 0.21 mmol) at r.t. for 16 h gave an
orange fraction, which was recrystallized from CH2Cl2/hexane to
give orange microcrystalline [RuCl(CϵCCO2Me)(PPh3)2(Bu2t bpy)]
(4) (112 mg, 53 %). Anal. Calcd for C58H57ClN2O2P2Ru (M ϭ
1012): C, 68.80; H, 5.67; N, 2.77. Found: C, 68.73; H, 5.72; N,
2.72 %.
Variata. For all specimens (unsolvated), even at 100 K, the data
range was seriously limited.
Compound 5 yielded the only determination unimpeded by serious
disorder; even so, the specimen suffered from a very broad mo-
saicity and yielded inferior residuals.
IR (nujol, cmϪ1): ν(CϵC) 2020, ν(CO 1915. 1H NMR (CDCl3): δ 1.36, 1.43
(s, 18H, But), 2.84 (s, 3H, CO2Me), 6.78, 7.73, 7.97, 8.07 (4 x d, 8H, Hbpy),
7.12Ϫ7.41 (m, 30H, ArH). 13C NMR (CDCl3): δ 30.56 (s, CMe3), 35.19 (s,
CMe3), 48.50 (s, CO2Me), 116.64, 117.07, 117.57, 122.90 (s, bpy), 127.79,
129.61, 133.42 (s, ArH), 154.23 (s, CO2Me). ES-MS (MeOH/NaOMe, m/z):
1035, [M ϩ Na]ϩ; 1012, Mϩ; 977, [MϪCl]ϩ. Electrochemistry (CH2Cl2):
E1 ϭ 0.47, E2 ϭ 0.88 V.
Compound 3: There are two independent (half-)molecules in the
asymmetric unit, both similarly disposed with respect to crystallo-
graphic mirror planes in space group P2/m which contain the bpy
ring planes and the ClRuCϵC-C···CN components. In molecule 1
the mirror plane also contains the CC(H3) components of the bpy
substituents; the phenyl ring and associated nitro group of the
alkyne substituent are disordered over orientations in and normal
to the mirror plane, occupancies of the two components being set
at 0.5 after trial refinement. For molecule 2, two of the phenyl
rings of the PPh3 ligand, and the But substituents were modelled
as disordered over pairs of sites, occupancies 0.5.
[RuCl(CϵCFc)(PPh3)2(Bu2t bipy)] (5). From 1 (100 mg, 0.10 mmol)
and HCϵCFc (31 mg, 0.15 mmol) in CH2Cl2 (15 ml) with Tl[PF6]
(36 mg, 0.10 mmol) at r.t. for 3 d, and purification by column chro-
matography and preparative t.l.c. plates, a red fraction (acetone-
hexane, 2/3) (Rf ϭ 0.6) was recrystallised from CH2Cl2/hexane to
give red microcrystalline [RuCl(CϵCFc)(PPh3)2(Bu2t bipy)] (5)
(48 mg, 42 %). Anal. Calcd for C66H63ClFeN2P2Ru (M ϭ 1138):
C, 69.58; H, 5.58; N, 2.46. Found: C, 69.67; H, 5.61; N, 2.50 %.
Compound 4: There are two independent molecules, devoid of crys-
tallographic symmetry, in the asymmetric unit; both are disordered.
In molecule 1, two of the phenyl rings of one of the PPh3 ligands,
and both But substituents are disordered over pairs of sites, the
disorder seemingly concerted, occupancies refining to 0.615(5) and
complement. Similar disorder is found in molecule 2 except that
only one But substituent was modelled as disordered, disorder oc-
IR (nujol, cmϪ1): ν(CϵC) 2066. 1H NMR (C6D6): δ 1.20 (s, 18H, But), 3.41,
4.04 (2 x m, 2 x 2H, C5H4), 3.57 (s, 5H, Cp), 6.97Ϫ7.79 (m, 36H, ArH). 13
C
NMR (C6D6): δ 25.21 (s, CMe3), 29.03 (s, CMe3), 66.79 (s, C5H4), 67.21 (s,
Cp), 109.37 (s, CϵC), 128.09Ϫ134.71 (m, Ar and ArH). ES-MS (MeOH,
m/z): 1161, [M ϩ Na]ϩ; 1138, Mϩ; 1103, [M-Cl]ϩ; 894, [MϪClϪCϵCFc]ϩ;
1100
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© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 1097Ϫ1101

Some Alkynyl-Ruthenium Complexes
cupancies throughout being set at 0.5 after trial refinement. Dis-
ordered phenyl ring components were modelled as rigid bodies in
the refinement, all disordered carbon atoms being refined with iso-
tropic displacement parameter forms.
[4] (a) T. J. Wadas, R. J. Lachicotte, R. Eisenberg, Inorg. Chem.
2003, 42, 3772; (b) J. E. McGarrah, Y.-J. Kim, M. Hissler,
R. Eisenberg, Inorg. Chem. 2001, 40, 4510; (c) M. Hissler,
W. B. Connick, D. K. Geiger, J. E. McGarrah, D. Lipa, R. J.
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Yellowlees, J. Chem. Soc., Dalton Trans. 2000, 63.
Supplementary Material. Full details of the structure determi-
nations (except structure factors) have been deposited with the
Cambridge Crystallographic Data Centre as CCDC 656221Ϫ
656223. Copies of this information may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (Fax:ϩ 44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk or
www:http://www.ccdc.cam.ac.uk).
[6] C. E. Whittle, J. A. Weinstein, M. W. George, K. S. Schanze,
Inorg. Chem. 2001, 40, 4053.
[7] (a) J. D. Lewis, J. N. Moore, Phys. Chem. Chem. Phys. 2004,
6, 4595; (b) J. D. Lewis, J. N. Moore, Dalton Trans. 2004, 1376.
[8] (a) S. H.-F. Chong, S. C.-F. Lam, V. W.-W. Yam, N. Zhu,
K.-K. Cheung, S. Fatallah, K. Costuas, J.-F. Halet, Organome-
tallics 2004, 23, 4924; (b) K. M.-C. Wong, S. C.-F. Lam,
C.-C. Ko, N. Zhu, V. W.-W. Yam, S. Roue, C. Lapinte, S. Fatal-
lah, K. Costuas, S. Kahlal, J.-F. Halet, Inorg. Chem. 2003, 42,
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Organomet. Chem. 2003, 670, 205.
Acknowledgements. We thank Professor Brian Nicholson (Univer-
sity 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.
[9] Q.-H. Wei, G.-Q. Yin, L.-Y. Zhang, Z.-N. Chen, Inorg. Chem.
2006, 45, 10371.
[10] C. J. Adams, S. J. A. Pope, Inorg. Chem. 2004, 43, 3492.
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m520.
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© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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