420
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
Osintseva et al.
(2%) of the [Ru4H(CO)6(pꢀMeC6H4C(O)C(H)=CPh]2[pꢀ
MeC6H3C(O)C(H)=C(H)Ph] complex, and 13.5 mg (3%) of the
Ru5(CO)11(µ ꢀO)(µ ꢀH)(pꢀMeC6H4C(O)C(H)=CPh)3 comꢀ
In addition to the hydride clusters H2Ru4(CO)13
,
H4Ru4(CO)12, and H2Ru6(CO)18, the following clusters
containing organic ligands were obtained: chain Ru3 (for
example, 3)4,7 and Ru4 (for example, 6) clusters,4,6
a butterflyꢀlike cluster Ru4,18 a Ru4 cluster consisting of
the Ru3 triangle and the quaternary ruthenium atom,
which is not directly bound to this triangle (5),4 a Ru5
cluster containing a dipperꢀtype metal core (1), a Ru6
cluster having a butterfly structure with two Ru atoms
occupying wingꢀtip positions (4),4 and a Ru6 cluster conꢀ
sisting of two fused quadrangles.* We observed the retenꢀ
tion of the triangular metal core only in the reaction with
cinnamaldehyde.10
4
3
plex (1). Complex 1. IR, n(CO)/cm–1 (hexane): 2070 s, 2046 s,
2032 v.s, 2018 m, 2012 m, 1990 w, 1976 m, 1966 s, 1958 w.
1H NMR of complex 1 (C6D6), d: –16.09 (d, 1 H, RuH, J =
1 Hz); 2.36, 2.38, and 2.43 (all s, 3 H each, CH3); 4.39 (d, 1 H,
C=CH, J = 1 Hz); 5.20 and 5.21 (both s, 1 H each, C=CH);
6.84—7.97 (m, 28 H, Ph). Found (%): C, 44.32; H, 2.65.
C59H40O15Ru5•CHCl3. Calculated (%): C, 44.66; H, 2.56. Small
darkꢀred needleꢀlike crystals were grown from a 1 : 2 chloroꢀ
form—hexane mixture.
Xꢀray diffraction study. Crystals of 1•2.5CHCl3 are triclinic,
C61.5H42.5Cl7.5O15Ru5, M = 1792.68, crystal dimensions
–
0.18×0.05×0.03 mm, space group P1, at 120 K a = 12.650(3) Å,
The transformation of Ru3(CO)12 follows two pathꢀ
ways. 1. The reaction affords polyhedral clusters (tetraꢀ
hedron, a trigonal bipyramid, and an octahedron) conꢀ
taining a rigid metal core consisting of the metal triangles
fused in different fashions.19 Among these complexes are
hydride complexes with carbonyl ligands and complexes
containing a minimum number of organic ligands. 2. The
presence of an organic ligand results in the formation of
monoꢀ or dinuclear species containing an organic ligand
(generally, the fiveꢀmembered oxaruthenacycle) in the
first steps of the process, and then these species are asꢀ
sembled to form polynuclear complexes. Strong interacꢀ
tions between the metal atoms can be absent from the
resulting complexes, and the charge redistribution occurs
through the bridging organic ligands. The metal cores of
the complexes can be flexible and adjust themselves to the
steric and electronic features of the organic ligand.
b = 13.517(3) Å, c = 22.098(5) Å, α = 97.432(6), β = 100.507(5),
γ = 117.156(4)°, V = 3207(1) Å3, Z = 2, dcalc = 1.857 g cm–3
,
µ(MoꢀKα) = 15.28 cm–1. The intensities of 26093 reflections
(11273 independent reflections, Rint = 0.097) were measured on
an automated Bruker SMART 1000 diffractometer equipped
with an area detector (graphite monochromator, λ(MoꢀKα) =
0.71073 Å, the ω scan step was 0.3°, the exposure time per frame
was 40 s, 2θmax = 50°). The structure was solved by direct methods
and refined by the fullꢀmatrix leastꢀsquares method against F 2
hkl
with anisotropic displacement parameters for all nonhydrogen
atoms. The crystal structure contains chloroform solvate molꢀ
ecules, two of which are disordered. The hydride ligand (H(1M)
atom) was located from a difference electron density map and
included in the final refinement with fixed atomic coordinates
and the isotropic displacement parameter. Other hydrogen atoms
were placed in geometrically calculated positions and refined
using a riding model. The final R factors were R1 = 0.0771
(refinement against Fhkl for 5321 reflections with I > 2σ(I )),
wR2 = 0.1806, and S = 0.966 (refinement against F 2 for all
hkl
independent reflections). All calculations were carried out on a
PC using the known program packages.20,21 The tables of atomic
coordinates, bond lengths, bond angles, and anisotropic disꢀ
placement parameters were deposited with the Cambridge Strucꢀ
tural Database.
Experimental
The 1H NMR spectra were recorded on a Bruker Avanceꢀ300
spectrometer (300.13 MHz) in C6D6 with the use of the residual
signal of incompletely deuterated C6D6 (δH 7.25) as the internal
standard. The IR spectra were measured on a Specordꢀ75 IR
spectrophotometer.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos 04ꢀ03ꢀ32371
and 03ꢀ03ꢀ32499).
3
Synthesis of tris[2,3,4ꢀη ꢀ4ꢀphenylꢀ2ꢀ(pꢀtolyl)ꢀ1ꢀoxabutaꢀ
1,3ꢀdiene]ꢀ(µ ꢀoxo)ꢀtri(µꢀhydrido)undecacarbonylpentarutheꢀ
4
nium (1). A solution of 3ꢀphenylꢀ1ꢀpꢀtolylprop2ꢀenꢀ1ꢀone
(444 mg, 2 mmol) in heptane (150 mL) was added to Ru3(CO)12
(320 mg, 0.5 mmol) and the reaction mixture was refluxed for 4 h.
After cooling to room temperature, the reaction mixture was
filtered. The filtrate was chromatographed on a silica gel colꢀ
umn. Elution with heptane afforded 9 mg of Ru3(CO)12 and 2 mg
of a mixture of Ru3(CO)12 and H4Ru4(CO)12. Elution with a
10 : 1 mixture of heptane and CH2Cl2 gave small amounts of the
H2Ru4(CO)13 and H2Ru6(CO)18 complexes, 11 mg (3%) of the
Ru2(CO)6(µꢀH)(pꢀMeC6H4C(O)C(H)=CPh) complex (2),
80 mg (18%) of the Ru3(CO)8(pꢀMeC6H4C(O)C(H)=CPh)2
complex (3), 5 mg (2%) of the Ru6(CO)12(µ ꢀCO)2(µ ꢀ
References
1. M. I. Bruce, Comprehensive Organometallic Chemistry,
Eds G. Wilkinson, F. G. A. Stone, and E. W. Abel, Pergamon
Press, Oxford, 1982, 4, 847.
2. R. K. Pomeroy, Comprehensive Organometallic Chemistry II,
Eds E. W. Abel, F. G. A. Stone, and G. Wilkinson, Pergamon
Press, Oxford, 1995, 7, 835.
3. S. P. Gubin, Khimiya klasterov [Cluster Chemistry], Ed. I. I.
Moiseev, Nauka, Moscow, 1987 (in Russian).
4. M. I. Rybinskaya, L. V. Rybin, S. V. Osintseva, F. M.
Dolgushin, A. I. Yanovsky, and Yu. T. Struchkov, Izv. Akad.
Nauk, Ser. Khim., 1995, 159 [Russ. Chem. Bull., 1995, 44,
154 (Engl. Transl.)].
2
4
O)(µ ꢀH)2(pꢀMeC6H4C(O)C(H)=CPh)2 complex (4), 9 mg
2
* The complex was synthesized by the reaction of Ru3(CO)12
with 2ꢀmethylꢀ3ꢀmorpholinoꢀ1ꢀphenylpropꢀ2ꢀenꢀ1ꢀone. The
results will be published elsewhere.
5. L. V. Rybin, S. V. Osintseva, E. A. Petrovskaya, A. Z.
Kreindlin, F. M. Dolgushin, A. I. Yanovsky, P. V. Petrovskii,
Osintseva
