Reactivity of the dimer [{Ru(η3:η3-C10H16)(μ- Cl)Cl}2] towards diphosphines and diphosphine-monoxides: Synthesis and characterization of novel (2,7-dimethylocta-2,6-diene-1,8-diyl)-ruthenium(IV) compl

Article abstract of DOI:10.1016/S0020-1693(02)01437-8

Treatment of complex [Ru(η³:η³-C₁₀H₁₆)Cl ₂(κ¹-P-Ph₂PCH₂PPh ₂)] (2) with AgBF₄ yields the chelate derivative [Ru(η³:η³-C

Full text of DOI:10.1016/S0020-1693(02)01437-8

Inorganica Chimica Acta 347 (2003) 41ꢁ48
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Reactivity of the dimer [{Ru(h3:h3-C10H16)(m-Cl)Cl}2] towards
diphosphines and diphosphine-monoxides: synthesis and
characterization of novel (2,7-dimethylocta-2,6-diene-1,8-diyl)-
ruthenium(IV) complexes
Victorio Cadierno, Sergio E. Garc´ıa-Garrido, Jose´ Gimeno *
Departamento de Qu´ımica Orga´nica e Inorga´nica, Facultad de Qu´ımica, Instituto Universitario de Qu´ımica Organometa´lica ‘Enrique Moles’
(Unidad Asociada al CSIC), Universidad de Oviedo, E-33071 Oviedo, Spain
Received 20 February 2002; accepted 13 May 2002
Dedicated to Professor Rafael Uso´n with great admiration for his outstanding contributions to modern inorganic chemistry
Abstract
Treatment of complex [Ru(h3:h3-C10H16)Cl2(k1-P-Ph2PCH2PPh2)] (2) with AgBF4 yields the chelate derivative [Ru(h3:h3-
C10H16)Cl(k2-P,P-Ph2PCH2PPh2)][BF4] (3). Attempts to generate species structurally related to 2 by reaction of the bis(allyl)-
ruthenium(IV) dimer [{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1) with diphosphines Ph2P(CH2)nPPh2 (nꢀ
/
2, 3, 4) failed, obtaining instead
2 (4a), 3 (4b), 4 (4c)). In contrast, mononuclear
1 (5a), 2 (5b), 3 (5c), 4 (5d)) have been easily prepared by
reaction of 1 with the corresponding diphosphine-monoxide Ph2P(CH2)nP(ÄO)Ph2 (nꢀ1, 2, 3, 4). Treatment of 5a,b with AgBF4
allows the formation of cationic derivatives [Ru(h3:h3-C10H16)Cl{k2-P,O-Ph2P(CH2)nP(Ä
O)Ph2}][BF4] (nꢀ1 (6a), 2 (6b)).
# 2002 Elsevier Science B.V. All rights reserved.
the dinuclear compounds [{Ru(h3:h3-C10H16)Cl2}2{m-Ph2P(CH2)nPPh2}] (nꢀ
neutral species [Ru(h3:h3-C10H16)Cl2{k1-P-Ph2P(CH2)nP(Ä
O)Ph2}] (nꢀ
/
/
/
/
/
/
/
Keywords: h3:h3-Octadienediyl complexes; Bis(allyl) complexes; Diphosphines; Diphosphine-monoxides; Ruthenium(IV) complexes
1. Introduction
diyl ligand (in solution complex 1 has been shown to
exist in two diasteromeric forms; see Fig. 1) [6]; and (iv)
the high reactivity derived from the chloro-bridged
structure. The later feature has disclosed wide series of
derivatives of the type: [Ru(h3:h3-C10H16)Cl2L] [6,7],
Although the dimeric chloro-bridged bis(allyl)-ruthe-
nium(IV) complex [{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1)
has been known for many years [1], its chemistry has
been scarcely developed. This fact is rather surprising
given the profusion of studies on the structurally related
ruthenium(II) dimers [{Ru(h6-arene)(m-Cl)Cl}2] [2].
Complex 1 and some of its derivatives possess a number
of features which make them particularly appealing.
These include: (i) remarkable stability and water solu-
bility [3]; (ii) catalytic activity in ROMP of cycloolefins
[3b,4] and butadiene polymerization [5]; (iii) the chirality
of the metal coordinated 2,7-dimethylocta-2,6-diene-1,8-
[Ru(h3:h3-C10H16)Cl(k2-Lꢁ
/L)]
[3a,8],
[{Ru(h3:h3-
C10H16)Cl2}2(m-L-L)] [7d,9] and [{Ru(h3:h3-C10H16)Cl-
(m-L)}2] [7e,10], generated by the bridging cleavage using
monodentate and bidentate ligands. In addition, catio-
nic species [Ru(h3:h3-C10H16)ClL2]ꢂ and [Ru(h3:h3-
C10H16)L3]2ꢂ have been also prepared by treatment of
1 with AgBF4 in the presence of monodentate ligands
[4d,7c,d,8f,9b].
In spite of this versatile reactivity, studies focused on
the preparation of bis(allyl)-ruthenium(IV) complexes
containing chelating diphosphines starting from dimer 1
have been almost neglected. To the best of our knowl-
edge only the complex [Ru(h3:h3-C10H16)Cl(k2-
P,P-iPr2PCH2PiPr2)][BF4] is known [11]. This prompted
* Corresponding author. Tel.: ꢂ
446.
E-mail address: jgh@sauron.quimica.uniovi.es (J. Gimeno).
/
34-98-5103-461; fax: ꢂ34-98-5103-
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(02)01437-8

42
V. Cadierno et al. / Inorganica Chimica Acta 347 (2003) 41ꢁ48
/
Fig. 1. The two diastereomeric forms of [{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1).
us to study the reactivity of [{Ru(h3:h3-C10H16)(m-
Cl)Cl}2] (1) towards the chelating bis(diphenylphosphi-
no)alkane ligands Ph2P(CH2)nPPh2 (dppm, dppe, dppp
and dppb), as well as their hemilabile diphosphine-
2.2. Preparations
2.2.1. [Ru(h3:h3-C10H16)Cl(k2-P,P-
Ph2PCH2PPh2)][BF4] (3)
Method A: a suspension of 0.200 g (0.289 mmol) of
[Ru(h3:h3-C10H16)Cl2(k1-P-Ph2PCH2PPh2)] (2) and
0.058 g (0.298 mmol) of AgBF4 in 10 ml of dichlor-
omethane was stirred in the dark, at room temperature
(r.t.), for 30 min. The reaction mixture was then filtered
through Kieselguhr and the filtrate evaporated to
dryness. The resulting yellow solid residue was washed
monoxide counterparts Ph2P(CH2)nP(Ä
/O)Ph2 (dppmO,
dppeO, dpppO and dppbO).
2. Experimental
with diethyl ether (3ꢃ20 ml) and dried in vacuo. Yield
/
0.187 g (87%). Anal. Calc. for RuC35H38F4P2BCl
(744.12 g molꢄ1): C, 56.51; H, 5.15. Found: C, 56.26;
2.1. General information
H, 4.89%. IR (KBr, cmꢄ1): nꢀ
3055 (m), 2915 (m), 1628
(m), 1484 (m), 1435 (s), 1385 (w), 1060 (vs), 998 (m), 741
/
The manipulations were performed under an atmos-
phere of dry nitrogen using vacuum-line and standard
Schlenk techniques. Solvents were dried by standard
methods and distilled under nitrogen before use. All
reagents were obtained from commercial suppliers and
used without further purification with the exception of
compounds [{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1) [5],
[Ru(h3:h3-C10H16)Cl2(k1-P-Ph2PCH2PPh2)] (2) [9a],
dppmO [12], dppeO [12], dpppO [12] and dppbO [12]
which were prepared by following the methods reported
in the literature. Infrared spectra were recorded on a
(s), 696 (s), 532 (m), 510 (m), 483 (s); 31P{1H} NMR
((CD3)2CO) dꢀ
Hz) ppm; 1H NMR ((CD3)2CO) dꢀ
J(H,P)ꢀ1.7 Hz, J(H,P)ꢀ1.7 Hz, CH3), 2.40 (dd, 1H,
J(H,P)ꢀ15.0 Hz, J(H,P)ꢀ4.5 Hz, H2 or H10), 2.51 (d,
3H, J(H,P)ꢀ2.0 Hz, CH3), 2.61 (dd, 1H, J(H,P)ꢀ9.1
Hz, J(H,P)ꢀ4.5 Hz, H2 or H10), 2.75, 3.03, 3.24 and
3.40 (m, 1H each, H4, H5, H6 and H7), 3.51 (dd, 1H,
J(H,P)ꢀ3.9 Hz, J(H,P)ꢀ3.9 Hz, H1 or H9), 3.85 and
4.92 (m, 1H each, H3 and H8), 4.14 (dd, 1H, J(H,P)ꢀ
4.3 Hz, J(H,P)ꢀ4.3 Hz, H1 or H9), 5.34 (m, 2H,
PCH2P), 6.50ꢁ
8.30 (m, 20H, Ph) ppm; 13C{1H} NMR
((CD3)2CO) dꢀ19.24 (dd, J(C,P)ꢀ3.8 Hz, J(C,P)ꢀ
1.3 Hz, CH3), 19.74 (d, J(C,P)ꢀ1.3 Hz, CH3), 31.06
and 37.84 (s, C4 and C5), 38.82 (dd, J(C,P)ꢀ28.0 Hz,
J(C,P)ꢀ28.0 Hz, PCH2P), 67.99 (dd, J(C,P)ꢀ5.7 Hz,
J(C,P)ꢀ2.5 Hz, C1 or C8), 69.05 (d, J(C,P)ꢀ5.7 Hz,
C1 or C8), 98.18 (dd, J(C,P)ꢀ3.5 Hz, J(C,P)ꢀ1.6 Hz,
C3 and C6), 113.46 (dd, J(C,P)ꢀ2.5 Hz, J(C,P)ꢀ2.5
Hz, C2 or C7), 116.56 (s, C2 or C7), 117.00ꢁ133.00 (m,
Ph) ppm.
/
ꢄ
/
33.70 and ꢄ
/
15.84 (d, J(P,P)ꢀ
/58.2
/1.87 (dd, 3H,
/
/
/
/
/
/
/
/
/
/
/
Perkinꢁ
/
Elmer 1720-XFT spectrometer. The C and H
Elmer 2400
/
analyses were carried out with a Perkinꢁ
/
/
/
/
microanalyzer. NMR spectra were recorded on a Bruker
DPX-300 instrument at 300 MHz (1H), 121.44 MHz
(31P) or 75.47 MHz (13C) using SiMe4 or 85% H3PO4 as
standards. DEPT experiments have been carried out for
all the compounds reported.
/
/
/
/
/
/
/
/
The numbering for protons and carbons of the
octadienediyl skeleton is as follows:
/
/
/
Method B: a suspension of 0.200 g (0.324 mmol) of
[{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1), 0.250 g (0.650 mmol)
of dppm and 0.126 g (0.650 mmol) of AgBF4 in 10 ml of
dichloromethane was stirred in the dark, at r.t. for 30
min. The reaction mixture was then filtered through
Kieselguhr and the filtrate evaporated to dryness. The
resulting yellow solid residue was washed with diethyl

V. Cadierno et al. / Inorganica Chimica Acta 347 (2003) 41ꢁ
/48
43
ether (3ꢃ
(85%).
/
20 ml) and dried in vacuo. Yield 0.410 g
H1 and H9), 5.09 (m, 4H, H3 and H8), 7.30ꢁ
20H, Ph) ppm; 13C{1H} NMR (CD2Cl2) dꢀ
CH3), 26.45 (d, J(C,P)ꢀ
J(C,P)ꢀ5.7 Hz, PCH2CH2), 37.04 (s, C4 and C5), 66.77
(d, J(C,P)ꢀ5.7 Hz, C1 and C8), 108.17 (d, J(C,P)ꢀ9.5
Hz, C3 and C6), 124.93 (s, C2 and C7), 127.50ꢁ137.00
(m, Ph) ppm.
/
7.70 (m,
/20.92 (s,
/
27.3 Hz, PCH2), 26.46 (d,
/
2.2.2. [{Ru(h3:h3-C10H16)Cl2}2{m-Ph2P(CH2)nPPh2}]
2 (4a), 3 (4b), 4 (4c))
/
/
(nꢀ
/
/
A solution of 0.200 g (0.324 mmol) of [{Ru(h3:h3-
C10H16)(m-Cl)Cl}2] (1) in 10 ml of dichloromethane was
treated at r.t. with the corresponding diphosphine (0.325
mmol). After stirring for 5 min, the solvent was removed
under vacuum and the resulting solid residue washed
2.2.3. [Ru(h3:h3-C10H16)Cl2{k1-P-Ph2P(CH2)nP(Ä
1 (5a), 2 (5b), 3 (5c), 4 (5d))
/
O)Ph2}] (nꢀ
/
A solution of 0.400 g (0.648 mmol) of [{Ru(h3:h3-
C10H16)(m-Cl)Cl}2] (1) in 10 ml of dichloromethane was
treated at r.t. with the corresponding diphosphine-
monoxide (1.298 mmol). After stirring for 5 min, the
solvent was removed under vacuum and the resulting
with hexanes (3ꢃ20 ml) and dried in vacuo. 4a: yellow
/
solid; yield 0.319 g (97%). Anal. Calc. for Ru2C46H56-
Cl4P2 (1014.85 g molꢄ1): C, 54.44; H, 5.53. Found: C,
53.96; H, 5.25%. IR (KBr, cmꢄ1): nꢀ
3052 (m), 2853
(m), 1587 (w), 1432 (s), 1383 (s), 1311 (w), 1185 (m),
/
solid residue washed with diethyl ether (3ꢃ20 ml) and
/
1087 (m), 1023 (m), 969 (m), 861 (m), 749 (m), 694 (vs),
529 (s), 519 (s), 491 (m); 31P{1H} NMR (CD2Cl2) dꢀ
dried in vacuo. 5a: orange solid; yield 0.883 g (96%).
Anal. Calc. for RuC35H38Cl2P2O (708.61 g molꢄ1): C,
59.32; H, 5.40. Found: C, 59.15; H, 5.41%. IR (KBr,
/
24.97 and 25.30 (s) ppm; 1H NMR (CD2Cl2) dꢀ
2.06 (s,
/
12H, CH3), 2.34 and 2.70 (m, 2H each, P(CH2)2P), 2.59
(m, 4H, H4 and H6), 2.97 and 3.01 (br, 2H each, H2 and
H10), 3.37 (m, 4H, H5 and H7), 3.96 and 4.03 (d, 2H
cmꢄ1): nꢀ
3050 (w), 2854 (w), 1587 (w), 1483 (m), 1434
/
(s), 1383 (m), 1310 (m), 1202 (vs), 1173 (s), 1115 (vs),
1024 (m), 996 (w), 920 (w), 851 (w), 802 (s), 736 (vs), 691
(vs), 615 (w), 552 (m), 506 (s), 487 (s); 31P{1H} NMR
each, J(H,P)ꢀ
H8), 7.30ꢁ
7.65 (m, 20H, Ph) ppm; 13C{1H} NMR
(CD2Cl2) dꢀ20.87 (s, CH3), 22.84 (m, P(CH2)2P),
36.95 and 36.99 (s, C4 and C5), 66.77 (s, C1 and C8),
108.23 and 108.37 (d, J(C,P)ꢀ5.4 Hz, C3 and C6),
124.90 (d, J(C,P)ꢀ7.0 Hz, C2 and C7), 127.00ꢁ136.00
/7.7 Hz, H1 and H9), 5.05 (m, 4H, H3 and
/
(CD2Cl2) dꢀ
(d, J(P,P)ꢀ29.5 Hz, Ph2PÄ
dꢀ2.14 (s, 6H, CH3), 2.64 (m, 2H, H4 and H6), 3.29 (d,
2H, J(H,P)ꢀ3.1 Hz, H2 and H10), 3.47 (m, 2H, H5 and
H7), 3.79 and 4.15 (m, 1H each, PCH2PÄO), 4.24 (d, 2H,
J(H,P)ꢀ9.6 Hz, H1 and H9), 5.20 (m, 2H, H3 and H8),
7.00ꢁ
7.80 (m, 20H, Ph) ppm; 13C{1H} NMR (CD2Cl2)
dꢀ20.86 (s, CH3), 26.13 (dd, J(C,P)ꢀ61.8 Hz,
J(C,P)ꢀ18.5 Hz, PCH2PÄO), 36.89 (s, C4 and C5),
68.45 (d, J(C,P)ꢀ4.9 Hz, C1 and C8), 107.85 (d,
J(C,P)ꢀ10.3 Hz, C3 and C6), 125.73 (d, J(C,P)ꢀ1.2
Hz, C2 and C7), 127.10ꢁ136.40 (m, Ph) ppm. 5b: orange
solid; yield 0.853 (91%). Anal. Calc. for
RuC36H40Cl2P2O (722.64 g molꢄ1): C, 59.83; H, 5.58.
Found: C, 59.56; H, 5.80%. IR (KBr, cmꢄ1): nꢀ
3057
/
18.61 (d, J(P,P)ꢀ
/
29.5 Hz, Ph2P), 22.80
/
/
/
O) ppm; 1H NMR (CD2Cl2)
/
/
/
/
/
/
(m, Ph) ppm. 4b: orange solid; yield 0.313 g (94%). Anal.
Calc. for Ru2C47H58Cl4P2 (1028.87 g molꢄ1): C, 54.87;
H, 5.68. Found: C, 54.81; H, 5.64%. IR (KBr, cmꢄ1):
/
/
/
/
nꢀ/3054 (m), 2908 (m), 1672 (m), 1433 (s), 1382 (s), 1186
/
/
(m), 1087 (m), 1019 (m), 959 (s), 857 (m), 789 (w), 742
(s), 695 (vs), 525 (s), 493 (s); 31P{1H} NMR (CD2Cl2)
/
/
/
1
dꢀ
/
16.05 and 16.69 (s) ppm; H NMR (CD2Cl2) d ꢀ
/
/
1.30 (m, 2H, CH2CH2CH2), 2.11 and 2.13 (s, 6H each,
CH3), 2.63 (m, 4H, H4 and H6), 2.81 (m, 4H, PCH2),
g
2.94 and 3.03 (d, J(H,P)ꢀ
4H, H5 and H7), 4.03 and 4.05 (d, 2H each, J(H,P)ꢀ
Hz, H1 and H9), 5.09 (m, 4H, H3 and H8), 7.25ꢁ7.75 (m,
20H, Ph) ppm; 13C{1H} NMR (CD2Cl2) dꢀ
20.06 (s,
CH2CH2CH2), 20.87 (s, CH3), 27.72 (dd, J(C,P)ꢀ26.5
Hz, J(C,P)ꢀ12.2 Hz, PCH2), 37.01 (s, C4 and C5),
66.74 (s, C1 and C8), 108.09 and 108.21 (d, J(C,P)ꢀ9.8
Hz, C3 and C6), 124.90 (s, C2 and C7), 127.00ꢁ137.00
/2.9 Hz, H2 and H10), 3.41 (m,
/
/9.2
(m), 2855 (m), 1590 (w), 1483 (m), 1434 (s), 1381 (m),
1278 (w), 1198 (s), 1174 (vs), 1121 (s), 1085 (s), 1026 (m),
967 (m), 881 (m), 860 (m), 788 (m), 733 (vs), 692 (vs),
545 (s), 517 (s), 501 (s), 482 (s); 31P{1H} NMR (CD2Cl2)
/
/
/
/
dꢀ
J(P,P)ꢀ
dꢀ2.14 (s, 6H, CH3), 2.21 and 3.44 (m, 2H each,
P(CH2)2PÄO), 2.64 (m, 2H, H4 and H6), 2.99 (m, 2H, H5
and H7), 3.07 (d, 2H, J(H,P)ꢀ3.5 Hz, H2 and H10),
4.17 (d, 2H, J(H,P)ꢀ9.4 Hz, H1 and H9), 5.13 (m,
2H, H3 and H8), 7.36ꢁ
7.77 (m, 20H, Ph) ppm; 13C{1H}
NMR (CD2Cl2) dꢀ19.49 (dd, J(C,P)ꢀ25.4 Hz,
J(C,P)ꢀ3.1 Hz, PCH2), 20.86 (s, CH3), 24.90 (dd,
J(C,P)ꢀ68.0 Hz, J(C,P)ꢀ4.5 Hz, CH2PÄO), 37.04
(s, C4 and C5), 66.56 (d, J(C,P)ꢀ5.4 Hz, C1 and
C8), 108.74 (d, J(C,P)ꢀ9.9 Hz, C3 and C6), 125.14
(d, J(C,P)ꢀ1.2 Hz, C2 and C7), 128.00ꢁ137.00 (m,
Ph) ppm. 5c: yellow solid; yield 0.937
/
20.19 (d, J(P,P)ꢀ
39.1 Hz, Ph2PÄ
/
/
39.1 Hz, Ph2P), 31.79 (d,
1
/
/
/O) ppm; H NMR (CD2Cl2)
/
(m, Ph) ppm. 4c: yellow solid; yield 0.321 g (95%). Anal.
Calc. for Ru2C48H60Cl4P2 (1042.91 g molꢄ1): C, 55.28;
H, 5.79. Found: C, 54.99; H, 5.73%. IR (KBr, cmꢄ1):
/
/
/
nꢀ/3055 (m), 2902 (m), 2853 (m), 1573 (w), 1462 (m),
/
1434 (s), 1381 (s), 1183 (w), 1159 (w), 1096 (m), 1047 (w),
/
/
1022 (m), 962 (w), 859 (m), 846 (m), 748 (s), 696 (vs), 523
/
(s), 495 (s); 31P{1H} NMR (CD2Cl2) dꢀ
/
17.73 and 17.83
1.40 and 2.49 (m,
4H each, P(CH2)4P), 2.11 (s, 12H, CH3), 2.61 (m, 4H,
H4 and H6), 3.05 (d, 4H, J(H,P)ꢀ3.2 Hz, H2 and H10),
3.40 (m, 4H, H5 and H7), 4.09 (d, 4H, J(H,P)ꢀ9.4 Hz,
/
/
/
(s) ppm; 1H NMR (CD2Cl2) dꢀ
/
1.00ꢁ
/
/
/
/
/
/
/

44
V. Cadierno et al. / Inorganica Chimica Acta 347 (2003) 41ꢁ48
/
g (98%). Anal. Calc. for RuC37H42Cl2P2O (736.66 g
molꢄ1): C, 60.33; H, 5.75. Found: C, 60.34; H,
0.720 g (83%). Anal. Calc. for RuC35H38F4P2BClO
(759.96 g molꢄ1): C, 55.31; H, 5.04. Found: C, 55.05;
5.20%. IR (KBr, cmꢄ1): nꢀ
3052 (m), 2914 (m), 1586
/
H, 4.85%. IR (KBr, cmꢄ1): nꢀ
3054 (w), 2859 (m), 1623
(w), 1485 (d), 1438 (s), 1388 (w), 1134 (vs), 1058 (vs), 859
/
(w), 1483 (m), 1435 (s), 1382 (m), 1310 (w), 1243
(w), 1187 (vs), 1160 (s), 1118 (s), 1101 (m), 1021
(m), 951 (m), 859 (m), 791 (w), 743 (s), 716 (vs),
697 (vs), 522 (s), 521 (s), 482 (s); 31P{1H} NMR
(w), 786 (m), 742 (s), 699 (s), 547 (s), 514 (s), 465 (m);
31P{1H} NMR (CD2Cl2) dꢀ
/
26.19 (d, J(P,P)ꢀ
28.3 Hz, Ph2PÄO) ppm; H
1.70 and 2.18 (s, 3H each, CH3),
2.57 (d, 1H, J(H,P)ꢀ5.4 Hz, H2 or H10), 3.02 (m, 2H,
H4 and H6), 3.31 (d, 1H, J(H,P)ꢀ2.8 Hz, H2 or H10),
3.73 (m, 2H, H5 and H7), 3.95 (d, 2H, J(H,P)ꢀ9.4 Hz,
H1 and H9), 4.29 (m, 2H, PCH2PÄO), 5.01 and 5.31 (m,
1H each, H3 and H8), 7.30ꢁ8.05 (m, 20H, Ph) ppm;
13C{1H} NMR (CD2Cl2) dꢀ
20.52 and 20.78 (s, CH3),
28.08 (dd, J(C,P)ꢀ67.1 Hz, J(C,P)ꢀ15.9 Hz, PCH2PÄ
O), 36.96 and 37.77 (s, C4 and C5), 68.25 (d, J(C,P)ꢀ
3.2 Hz, C1 or C8), 68.32 (d, J(C,P)ꢀ3.0 Hz, C1 or C8),
109.59 (dd, J(C,P)ꢀ7.9 Hz, J(C,P)ꢀ2.5 Hz, C3 or C6),
118.04 (d, J(C,P)ꢀ10.8 Hz, C3 or C6), 125.99 (d,
J(C,P)ꢀ1.9 Hz, C2 or C7), 126.35 (d, J(C,P)ꢀ1.3
Hz, C2 or C7), 129.00ꢁ136.00 (m, Ph) ppm. 6b: yellow
solid; yield 0.750 (85%). Anal. Calc. for
RuC36H40F4P2BClO (773.99 g molꢄ1): C, 55.86; H,
5.21. Found: C, 55.64; H, 5.38%. IR (KBr, cmꢄ1): nꢀ
/
28.3 Hz,
1
Ph2P), 72.08 (d, J(P,P)ꢀ
/
/
(CD2Cl2) dꢀ
31.04 (d, J(P,P)ꢀ
(CD2Cl2) dꢀ1.39 and 1.58 (m, 1H each, CH2CH2CH2),
2.10 (s, 6H, CH3), 2.25 and 2.84 (m, 2H each, PCH2
and CH2PÄO), 2.61 (m, 2H, H4 and H6), 3.01 (d, 2H,
J(H,P)ꢀ3.1 Hz, H2 and H10), 3.40 (m, 2H, H5 and
H7), 4.08 (d, 2H, J(H,P)ꢀ9.4 Hz, H1 and H9), 5.09
(m, 2H, H3 and H8), 7.20ꢁ7.80 (m, 20H, Ph)
ppm; 13C{1H} NMR (CD2Cl2) dꢀ
17.72 (dd,
J(C,P)ꢀ3.8 Hz, J(C,P)ꢀ3.8 Hz, CH2CH2CH2),
20.89 (s, CH3), 27.72 (dd, J(C,P)ꢀ26.1 Hz, J(C,P)ꢀ
12.7 Hz, PCH2), 30.89 (dd, J(C,P)ꢀ70.6 Hz, J(C,P)ꢀ
12.1 Hz, CH2PÄO), 37.03 (s, C4 and C5), 66.78 (d,
J(C,P)ꢀ5.7 Hz, C1 and C8), 108.19 (d, J(C,P)ꢀ9.5 Hz,
C3 and C6), 125.04 (s, C2 and C7), 128.00ꢁ136.00 (m,
/
17.53 (d, J(P,P)ꢀ
/
1.9 Hz, Ph2P),
NMR (CD2Cl2) dꢀ
/
/
1.9 Hz, Ph2PÄ
/
O) ppm; 1H NMR
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
g
Ph) ppm. 5d: orange solid; yield 0.935 g (96%). Anal.
Calc. for RuC38H44Cl2P2O (750.69 g molꢄ1): C, 60.80;
H, 5.91. Found: C, 60.65; H, 6.00%. IR (KBr, cmꢄ1):
/
3054 (m), 2859 (m), 1589 (w), 1486 (m), 1437 (s), 1383
(m), 1280 (w), 1128 (s), 1062 (vs), 978 (s), 860 (w), 742
(s), 724 (s), 693 (s), 551 (s), 509 (s), 485 (m); 31P{1H}
nꢀ3054 (w), 2902 (w), 1591 (w), 1482 (m), 1451 (w),
/
1436 (m), 1379 (m), 1311 (w), 1291 (w), 1242 (w),
1197 (s), 1117 (s), 1087 (s), 1071 (m), 1024 (m), 995
(m), 965 (m), 921 (w), 886 (w), 857 (m), 839 (m), 789 (m),
781 (m), 745 (s), 720 (s), 714 (s), 699 (s), 551 (s), 517
NMR (CD2Cl2) dꢀ
52.53 (d, J(P,P)ꢀ2.3 Hz, Ph2PÄ
(CD2Cl2) dꢀ1.59 and 2.19 (s, 3H each, CH3), 2.78 (m,
2H, H4 and H6), 2.83 (d, 1H, J(H,P)ꢀ3.7 Hz, H2 or
H10), 2.93 (d, 1H, J(H,P)ꢀ3.1 Hz, H2 or H10), 3.12 (m,
2H, H5 and H7), 3.33 and 3.74 (m, 2H each, P(CH2)2PÄ
O), 4.25 (d, 1H, J(H,P)ꢀ9.9 Hz, H1 or H9), 4.49 (d, 1H,
J(H,P)ꢀ11.1 Hz, H1 or H9), 5.04 and 5.32 (m, 1H each,
H3 and H8), 7.20ꢁ
8.10 (m, 20H, Ph) ppm; 13C{1H}
NMR (CD2Cl2) dꢀ16.42 (dd, J(C,P)ꢀ28.0 Hz,
J(C,P)ꢀ5.7 Hz, PCH2), 18.93 (d, J(C,P)ꢀ66.7 Hz,
CH2PÄO), 20.45 (s, CH3), 21.92 (d, J(C,P)ꢀ0.6 Hz,
CH3), 36.98 and 38.17 (s, C4 and C5), 67.96 (d, J(C,P)ꢀ
3.8 Hz, C1 or C8), 68.03 (d, J(C,P)ꢀ3.2 Hz, C1 or C8),
111.33 (d, J(C,P)ꢀ7.0 Hz, C3 or C6), 118.17 (d,
J(C,P)ꢀ10.2 Hz, C3 or C6), 127.06 (d, J(C,P)ꢀ1.3
Hz, C2 or C7), 127.99 (d, J(C,P)ꢀ1.9 Hz, C2 or C7),
128.50ꢁ134.50 (m, Ph) ppm.
/
9.33 (d, J(P,P)ꢀ
/
2.3 Hz, Ph2P),
/
/
O) ppm; 1H NMR
/
(s), 488 (s); 31P{1H} NMR (CD2Cl2) dꢀ
/
17.42 (s, Ph2P),
O) ppm; H NMR (CD2Cl2) dꢀ0.87ꢁ
1.65 (m, 6H, P(CH2)4PÄO), 2.15 (s, 6H, CH3), 2.63
(m, 2H, H4 and H6), 2.80 (m, 2H, P(CH2)4PÄO), 3.14
(br, 2H, H2 and H10), 3.44 (m, 2H, H5 and H7), 4.13 (d,
2H, J(H,P)ꢀ9.3 Hz, H1 and H9), 5.16 (m, 2H, H3
and H8), 7.30ꢁ
7.70 (m, 20H, Ph) ppm; 13C{1H}
NMR (CD2Cl2) dꢀ20.96 (s, CH3), 23.39 (dd,
J(C,P)ꢀ12.8 Hz, J(C,P)ꢀ2.4 Hz, CH2CH2PÄO),
26.05 (dd, J(C,P)ꢀ15.9 Hz, J(C,P)ꢀ4.9 Hz,
PCH2CH2), 26.56 (d, J(C,P)ꢀ26.9 Hz, PCH2), 29.60
(d, J(C,P)ꢀ70.8 Hz, CH2PÄO), 37.06 (s, C4 and C5),
66.75 (d, J(C,P)ꢀ4.9 Hz, C1 and C8), 108.21 (d,
J(C,P)ꢀ9.8 Hz, C3 and C6), 124.95 (s, C2 and C7),
128.00ꢁ137.00 (m, Ph) ppm.
/
1
30.78 (s, Ph2PÄ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Method B: a suspension of 0.200 g (0.324 mmol) of
[{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1), the corresponding
2.2.4. [Ru(h3:h3-C10H16)Cl{k2-P,O-Ph2P(CH2)nP(Ä
O)Ph2}][BF4] (nꢀ1 (6a), 2 (6b))
/
diphosphine-monoxide (0.650 mmol) and 0.126
g
/
(0.650 mmol) of AgBF4 in 10 ml of dichloromethane
was stirred in the dark at r.t. for 30 min. The reaction
mixture was then filtered through Kieselguhr and the
filtrate evaporated to dryness. The resulting solid
Method A: a suspension of complexes 5a,b (1.141
mmol) and 0.224 g (1.150 mmol) of AgBF4 in 10 ml of
dichloromethane was stirred in the dark at r.t. for 30
min. The reaction mixture was then filtered through
Kieselguhr and the filtrate concentrated to dryness. The
resulting solid residue was washed with diethyl ether
residue was washed with diethyl ether (3ꢃ20 ml) and
/
dried in vacuo. 6a: yield 0.394 g (80%). 6b: yield 0.411 g
(82%).
(3ꢃ
/
20 ml) and dried in vacuo. 6a: orange solid; yield

V. Cadierno et al. / Inorganica Chimica Acta 347 (2003) 41ꢁ
/48
45
3. Results and discussion
trigonal-bipyramidal ruthenium atom. 13C{1H} NMR
spectrum also shows clearly that the two halves of the
octadienediyl ligand are in inequivalent environments
since nine different signals are observed (see Section 2).
To extend the scope of this reactivity we decided to
use the commercially available related diphosphines 1,2-
bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenyl-
phosphino)propane (dppp) and 1,4-bis(diphenylphos-
phino)butane (dppb). However, the treatment of 1
with 2 equiv. of these ligands, in dichloromethane at
room temperature, does not afford the desired mono-
nuclear derivatives [Ru(h3:h3-C10H16)Cl2{k1-P-Ph2P-
3.1. Reactivity of [{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1)
towards diphosphines Ph2P(CH2)nPPh2 (nꢀ
/
1ꢁ4)
/
A preliminary account on the reactivity of the dimeric
bis(allyl)-ruthenium(IV) complex [{Ru(h3:h3-C10H16)-
(m-Cl)Cl}2] (1) towards bis(diphenylphosphino)methane
(dppm) was reported by Toerien and van Rooyen in
1991 [9a]. They reported that the dinuclear derivative
[{Ru(h3:h3-C10H16)Cl2}2(m-Ph2PCH2PPh2)], bearing a
bridging dppm unit, or the mononuclear adduct
[Ru(h3:h3-C10H16)Cl2(k1-P-Ph2PCH2PPh2)], in which
dppm is acting as a monodentate ligand, can be
selectively obtained depending exclusively on the molar
ratio used.
(CH2)nPPh2}] (nꢀ
mixtures containing the dinuclear species [{Ru(h3:h3-
C10H16)Cl2}2{m-Ph2P(CH2)nPPh2}] (nꢀ2 (4a), 3 (4b), 4
/2, 3, 4) obtaining instead reaction
/
(4c)) and the corresponding unreacted diphosphine.
Similar results were also observed when a large excess
(ca. 10 equiv.) of the ligands was used. As expected,
We have found that [Ru(h3:h3-C10H16)Cl2(k1-P-
Ph2PCH2PPh2)] (2) reacts with an stoichiometric
amount of AgBF4, in dichloromethane at room tem-
perature, to afford the cationic chelate complex
[Ru(h3:h3-C10H16)Cl(k2-P,P-Ph2PCH2PPh2)][BF4] (3)
which is isolated from the reaction mixture after
filtration of the AgCl formed (87% yield; Scheme 1).
Alternatively, 3 can be also prepared directly from
[{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1) by treatment with 2
equiv. of dppm and AgBF4 in dichloromethane.
Characterization of 3 was achieved unequivocally by
means of standard spectroscopic techniques (IR and
complexes 4aꢁ
under stoichiometric conditions (94ꢁ
2).
Compounds 4aꢁ
/
c can be properly prepared working
/
97% yield; Scheme
/c are air stable in the solid state and
soluble in polar solvents (e.g. dichloromethane or
acetone). They have been characterized by elemental
1
analyses and IR and NMR (31P{1H}, H and 13C{1H})
spectroscopy (for details see Section 2) being their
dimeric nature confirmed by the relative intensities of
the octadienediyl and diphosphine resonances (2:1) in
the 1H NMR spectra. Significantly, a closer examination
1
31P{1H}, H, and 13C{1H} NMR) as well as elemental
analyses (see Section 2). Thus, the 31P{1H} NMR
spectrum exhibits resonances consistent with an AB
of the NMR data of 4aꢁc reveals the presence of two
/
different isomers in solution. This fact is clearly
evidenced from: (a) the 31P{1H} NMR spectra which
show in all the cases the presence of two singlet signals
in ca. 1:1 ratio (4a: 24.97 and 25.30 ppm; 4b: 16.05 and
16.69 ppm; 4c: 17.73 and 17.83 ppm); and (b) the 1H and
13C{1H} NMR spectra in which a doubling of some
proton and carbon resonances is observed for the
octadienediyl ligand (see Section 2). We note that similar
results have been previously reported for the analogous
complexes [{Ru(h3:h3-C10H16)Cl2}2(m-dppm)] [9a] and
spin system (d ꢄ
/
33.70 and ꢄ
/
15.84 ppm (JPP
ꢀ58.2
/
Hz)), the highly shielded chemical shifts observed being
comparable to those recently reported for the related
complex [Ru(h3:h3-C10H16)Cl(k2-P,P-iPr2PCH2PiPr2)]-
[BF4] [11]. The 1H NMR spectrum displays a character-
istic four-line pattern for the terminal allylic protons (d
2.40, 2.61, 3.51 and 4.14 ppm) and two separated signals
for the methyl substituents (d 1.87 and 2.51 ppm) of the
bis(allyl) unit indicative of inequivalent axial sites on the
Scheme 1. Synthesis of the complex [Ru(h3:h3-C10H16)Cl(k2-P,P-dppm)][BF4] (3).

46
V. Cadierno et al. / Inorganica Chimica Acta 347 (2003) 41ꢁ48
/
Scheme 2. Synthesis of the dinuclear complexes [{Ru(h3:h3-C10H16)Cl2}2{m-Ph2P(CH2)n PPh2}] (4aꢁ
c).
/
[{Ru(h3:h3-C10H16)Cl2}2(m-dppf)] (dppfꢀ
/
1,1?-bis(di-
and dppb. Moreover, the presence in these ligands of
both a soft (P) and a hard (O) donor center confers
hemilabile properties to their metal complexes of interest
in homogeneous catalysis [13].
phenylphosphino)ferrocene) [9c] which has been attrib-
uted, on the basis of variable-temperature NMR
experiments, to the presence of two conformational
isomers in solution.
As expected, complex 1 reacts with a twofold excess of
It is apparent that the selective formation of the
Ph2P(CH2)nP(Ä
/
O)Ph2 (dppmO (nꢀ
/
1), dppeO (nꢀ
/
2),
complex
(2) versus the dinuclear species [{Ru(h3:h3-C10H16)-
Cl2}2{m-Ph2P(CH2)nPPh2}] (nꢀ2 (4a), 3 (4b), 4 (4c))
[Ru(h3:h3-C10H16)Cl2(k1-P-Ph2PCH2PPh2)]
dpppO (nꢀ3) and dppbO (nꢀ
/
/4)), in dichloromethane
at room temperature, to generate the neutral mono-
nuclear adducts [Ru(h3:h3-C10H16)Cl2{k1-P-Ph2P-
/
indicates a different coordination ability of the dipho-
sphines, probably due to the steric requirements of the
bulky h3:h3-octadienediyl-Ru(IV) fragment. It seems
that the relatively close proximity of both metallic
fragments for dppm does not facilitate the formation
of dinuclear species, i.e. [{Ru(h3:h3-C10H16)Cl2}2(m-
dppm)] [9a], which however can be readily formed for
the longer chain diphosphines dppe, dppp and dppb. In
accordance with this hypothesis we have found that,
(CH2)nP(Ä
/
O)Ph2}] (nꢀ1 (5a), 2 (5b), 3 (5c), 4 (5d)) as
/
the result of the selective coordination of the diphenyl-
phosphino group on the Ru(IV) center (91ꢁ98% yield;
/
Scheme 3). It is worth mentioning that no dinuclear
bridged products were detected even when the reactions
were carried out with only 1 equiv. of the diphosphine-
monoxides obtaining instead equimolar mixtures of 5aꢁ
d and the precursor complex 1.
Complexes 5aꢁd have been isolated as yellowꢁorange
/
/
/
while 4aꢁ
c are unreactive towards PPh3, [{Ru(h3:h3-
/
air-stable solids and are soluble in chlorinated solvents
and tetrahydrofuran. They have been characterized by
C10H16)Cl2}2(m-dppm)] readily reacts with 1 equiv. of
PPh3, in dichloromethane at room temperature, to
afford an equimolar mixture containing complex
[Ru(h3:h3-C10H16)Cl2(k1-P-Ph2PCH2PPh2)] (2) and
[Ru(h3:h3-C10H16)Cl2(PPh3)] [7a] via partial dissocia-
tion of the dppm ligand in [{Ru(h3:h3-C10H16)Cl2}2(m-
dppm)].
elemental analyses and IR and NMR (31P{1H}, H and
1
13C{1H}) spectroscopy being all the data fully consistent
with the proposed formulations (see Section 2). Sig-
nificant features are: (i) (31P{1H} NMR) the expected
doublet (JPP
resonances for the Ph2P and Ph2PÄ
ranges d 17.42ꢁ20.19 and 22.80ꢁ31.79 ppm, respec-
ꢀ
/
1.9ꢁ
/
39.1 Hz; 5aꢁ/c) or singlet (5d)
/O groups in the
Finally, we note that all attempts to prepare cationic
[Ru(h3:h3-C10H16)Cl{k2-P,P-Ph2P(CH2)n-
/
/
/
tively, and (ii) (1H and 13C{1H} NMR) the presence of a
single set of signals for the two allylic moieties of the 2,7-
dimethylocta-2,6-diene-1,8-diyl ligand (i.e. only five
resonances are observed in 13C{1H} NMR spectra)
indicative of the formation of a simple equatorial adduct
[Ru(h3:h3-C10H16)Cl2L] with a local C2-symmetry for
the octadienediyl chain [6].
species
PPh2}][BF4] (nꢀ
2, 3, 4) by treatment of dimer 1 with
2 equiv. of the appropriate diphosphine and AgBF4 in
dichloromethane, acetone or acetonitrile have been
unsuccessful obtaining instead complicated mixtures of
uncharacterized products. Apparently, the tendency of
dppe, dppp and dppb to act as bridging ligands prevents
the formation of the desired chelate complexes.
Treatment of dichloromethane solutions of complexes
5a,b with 1 equiv. of AgBF4 results in the formation of
1
/2
/
3
3
3.2. Reactivity of [{Ru(h3:h3-C10H16)(m-Cl)Cl}2] (1)
cationic
derivatives
[Ru(h :h -C10H16)Cl{k-P,O-
1 (6a; 83% yield), 2
towards diphosphine-monoxides Ph2P(CH2)nP(Ä
/
O)Ph2
Ph2P(CH2)nP(Ä
/
O)Ph2}][BF4] (nꢀ
/
(nꢀ1ꢁ4)
/
/
(6b; 85% yield); Scheme 3). These complexes can be also
prepared in similar yields from 1 by reaction with 2
equiv. of the diphosphine-monoxide and AgBF4 in
dichloromethane at room temperature. NMR spectro-
scopic data (see Section 2 for details) provide significant
structural information. Thus, in the 31P{1H} NMR
spectra the chelating coordination of the diphosphine-
Taking into account the lower ability of diphosphine-
monoxides to act as intermetallic bridging ligands when
compared to the corresponding diphosphines, we be-
came interested in studying the reactivity of dimer 1
towards the monoxides derived from dppm, dppe, dppp

V. Cadierno et al. / Inorganica Chimica Acta 347 (2003) 41ꢁ
/48
47
Scheme 3. Synthesis of the complexes [Ru(h3:h3-C10H16)Cl{k2-P,O-Ph2P(CH2)n P(Ä
O)Ph2}][BF4] (6a,b).
/
monoxide ligands is marked by a large downfield shift in
the phosphoryl group resonances from the parent
C10H16)Cl(k2-P,P-Ph2PCH2PPh2)][BF4] and [Ru(h3:h3-
C10H16)Cl{k2-P,O-Ph2P(CH2)nP(Ä
O)Ph2}][BF4] (nꢀ1,
2), can be obtained from the readily available dimer
[{Ru(h3:h3-C10H16)(m-Cl)Cl}2] via initial chloride brid-
ging cleavage to form neutral mononuclear species, i.e.
/
/
compounds 5a,b (6a: 72.08 ppm (JPP
ꢀ/28.3 Hz); 6b:
52.53 ppm (JPP 2.3 Hz)) in spite of the fact that this
ꢀ
/
phosphorus is not directly bound to the metal. This
behaviour, which has been previously observed in other
[Ru(h3:h3-C10H16)Cl2(k1-P-Ph2PCH2PPh2)]
and
[Ru(h3:h3-C10H16)Cl2{k1-P-Ph2P(CH2)n P(Ä
(nꢀ1, 2), and subsequent chloride extraction using
metallic fragments [13cꢁ/h], can be attributed to deloca-
/
O)Ph2}]
lization of electron density in the ꢁ
/
PÄOꢁRuꢁ frame-
/
/
/
/
work. In contrast, the 31P NMR chemical shifts for the
directly bound Ph2P phosphorus atoms are less affected
by the ring closure appearing at d 26.19 (6a) and 9.33
(6b) ppm. 1H NMR spectra of 6a,b indicate that the two
halves of the 2,7-dimethylocta-2,6-diene-1,8-diyl ligand
are inequivalent, as expected for the loss of the C2-
symmetry (see Section 4). This is also clearly evidenced
from the 13C{1H} NMR spectra in which ten separate
signals are observed for the bis(allyl) unit.
silver(I) tetrafluoroborate. The former process is clearly
the key step on this synthetic procedure since the
formation of undesirable dinuclear ligand-bridged spe-
cies, i.e. [Ru(h3:h3-C10H16)Cl2{k1-P-Ph2P(CH2)nPPh2}]
(nꢀ2, 3, 4), avoids the chelation of the ligand.
/
Acknowledgements
Significantly, all attempts to form the corresponding
[Ru(h3:h3-C10H16)Cl{k2-P,O-
/
This work was supported by the Ministerio de Ciencia
y Tecnolog´ıa (MCyT) of Spain (Project BQU2000-0227)
and the EU (COST programme D12/0025/99). S.E.G.-
G. thanks the MCyT for the award of a Ph.D. grant.
cationic
Ph2P(CH2)nP(Ä
derivatives
/
O)Ph2}][BF4] (nꢀ3, 4) by treatment of
5c,d with AgBF4 or starting directly from 1 have been
unsuccessful obtaining instead mixtures of uncharacter-
ized products. This behaviour can be attributed to the
lower thermodynamic stability of the seven and eight-
membered rings with respect to those of only five and six
members (6a,b).
References
[1] (a) L. Porri, M.C. Gallazzi, A. Colombo, G. Allegra, Tetrahedron
Lett. 47 (1965) 4187;
(b) L. Porri, G. Allegra, Acta Crystallogr., B 27 (1971) 1653.
[2] For a review on the chemistry of dimers [{Ru(h6-arene)(m-
Cl)Cl}2] see: H. Le Bozec, D. Touchard, P.H. Dixneuf, Adv.
Organomet. Chem. 29 (1989) 163.
4. Conclusions
[3] (a) S.O. Sommerer, G.J. Palenik, Organometallics 10 (1991) 1223;
(b) S. Wache, J. Organomet. Chem. 491 (1995) 235.
[4] (a) K. Hiraki, A. Kuroiwa, H. Hirai, J. Polym. Sci. A-19 (1971)
2323;
In summary, it has been demonstrated that cationic
mononuclear bis(allyl)-ruthenium(IV) complexes con-
taining chelating Pꢁ
/
P and Pꢁ
O ligands, i.e. [Ru(h3:h3-
/

48
V. Cadierno et al. / Inorganica Chimica Acta 347 (2003) 41ꢁ48
/
(b) L. Porri, R. Rossi, P. Diversi, A. Lucherini, Macromol. Chem.
175 (1974) 3097;
(f) G. Belchem, D.H.A. Schreiber, J.W. Steed, D.A. Tocher,
Inorg. Chim. Acta 218 (1994) 81.
[9] (a) J.G. Toerien, P.H. van Rooyen, J. Chem. Soc., Dalton Trans.
(1991) 2693;
(c) S. Wache, W.A. Herrmann, G. Artus, O. Nuyken, D. Wolf, J.
Organomet. Chem. 491 (1995) 181;
(b) J.W. Steed, D.A. Tocher, Polyhedron 11 (1992) 2729;
(c) V. Cadierno, S.E. Garc´ıa-Garrido, J. Gimeno, J. Organomet.
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