70
S. Ja¨a¨skela¨inen et al. / Journal of Organometallic Chemistry 633 (2001) 69–70
vents interactions between the tetranuclear [Rh2(CO)3-
(m-Cl)2{P(o-(CF3)Ph)3}]2 units and the growth of an
infinite chain.
The properties of the trifluoromethyl derivative of
triphenylphosphane make it suitable for controlling the
level of ligand substitution in Rh2(CO)4Cl2. The forma-
tion of a stable monosubstituted species is not typical;
the substitution with phosphanes usually proceeds fur-
ther. Even though the compound in solution appears to
be dimeric, in the solid state the dinuclear species are
coupled.
3. Supplementary material
Fig. 1. Structure of [Rh2(CO)3(m-Cl)2{P(o-(CF3)Ph)3}]2. Selected
bond distances (A) and angles (°): Rh(1)ꢀRh(2), 2.9753(3);
Rh(2)ꢀRh(2A), 3.2203(4); Rh(1)ꢀP(1), 2.2485(7); P(1)ꢀRh(1)ꢀRh(2),
120.99(2); Rh(1)ꢀRh(2)ꢀRh(2A), 123.66(11).
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 159196 for compound 1.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
,
The two Rh2(CO)3(m-Cl)2{P(o-(CF3)Ph)3}units are
linked by weak Rh–Rh interaction, where the dinuclear
units are joined with the RhꢀRhꢀRh angle of
123.66(11)°. The torsion angles Cl(1)ꢀRh(2)ꢀRh(2A)ꢀ
Cl(1A) and Rh(1)ꢀRh(2)ꢀRh(2A)ꢀRh(1A) are both
180.0° due to symmetry. The RhꢀRh distance within
References
,
the units is 2.9753(3) A, while the RhꢀRh distance
,
between the primary units (3.2203(4) A) is significantly
[1] A. Maisonnat, P. Kalck, R. Poilblanc, Inorg. Chem. 13 (1974)
661.
[2] J. Gallay, D. de Montauzon, R. Poilblanc, J. Organomet. Chem.
38 (1972) 179.
longer, indicating weaker metal–metal interaction. In
the solid state of the parent compound Rh2(CO)4(m-Cl)2
the molecules are ‘nearly bonded’; the intermolecular
,
[3] P. Serp, R. Feurer, R. Morancho, P. Kalck, J.-C. Daran, J.
Vaisserman, J. Organomet. Chem. 498 (1995) 41.
metalꢀmetal distance is longer than in 1 (3.324 A)
forming zig-zag chains [6]. Similarly, the chlorine
[4] The compound was formed by reaction between Rh2(CO)4Cl2 and
P(o-(CF3)Ph)3 in MeOH in Rh/L ratio 1:1 and successive crystal-
lization in CH2Cl2 at room temperature. IR (CH2Cl2, cm−1):
2093s, 2024s, 2008m. IR (KBr, cm−1): 2082s, 2028s, 2010vs.
31P-NMR (ppm): l=63.5 (d, 1JP–Rh=195 Hz). Owing to the
presence of small amounts of free ligand, as evidenced by NMR
spectroscopy, there were slight deviations from theoretical values
in the results of the elemental analysis.
,
bridged RhꢀRh bond is slightly longer (3.138 A) than
in 1. Thus, the inter- and intramolecular metal–metal
interactions in the parent compound are somewhat
weaker than the corresponding interactions in 1.
In the earlier reported structure of Rh2(CO)3(m-Cl)(m-
Cl/I)PPh3 [3] the intramolecular metal bond is
,
3.014(2)A, and thus only slightly longer than in 1, but
[5] Crystal data for [Rh2(CO)3(m-Cl)2{P(o-(CF3)Ph)3}]2: C48H24Cl4-
there is no interaction between the adjacent molecules.
Several phosphane substituted species with two to four
phosphane groups have been reported, and in
Rh2(CO)2Cl2(PMe2Ph)2, for example, the Rh···Rh dis-
F
18O6P2Rh4, M=1654.05, monoclinic, a=8.25540(10), b=
3
,
,
20.5824(3), c=15.8659(4) A, i=91.6300(10)°, V=2694.78(8) A ,
T=120 K, space group P21/c, Z=2, Dcalc=2.038 g cm−3, v
(Mo–Ka)=1.572 mm−1, 20 758 reflections collected, 5568 unique
(Rint=0.0343), no. parameters 418. The final R1 [I\2|(I)] was
0.0260 and wR2 was 0.0536. The largest difference peak and hole
,
tance is 3.167 A. This is comparable to the distances
(e A−3): 0.854 and −0.852. An orange plate-like crystal with
found in most other structures of bent di-m-chloro
complexes of Rh(I) and is considered as a weak metal–
metal interaction [7].
,
dimensions 0.30×0.20×0.05 mm was used. Data was collected
on a Nonius–Kappa CCD diffractometer. All non-hydrogen
atoms were refined anisotropically and phenyl hydrogens were
refined isotropically.
In 1, one carbonyl in each of the parent Rh2(CO)4(m-
Cl)2 units is replaced by a phosphane group. While the
phosphanes enhance metal–metal interaction and the
association of the primary units, their bulkiness pre-
[6] L. Walz, P. Scheer, Acta Crystallogr. Sect. C 47 (1991) 640.
[7] J.J. Bonnet, Y. Jeannin, P. Kalck, A. Maisonnat, R. Poilblanck,
Inorg. Chem. 14 (1975) 743.
.