Synthesis of a series of hexanuclear ruthenium carbido cluster alkynes under mild conditions: X-ray structure analyses of the complexes [Ru6C(CO)15(µ3-η2-PhCCH)] and [Ru6C(CO)15(µ3-η2-PhCCMe)]

The reaction of [Ru6C(CO)16]2–(1) with alkynes in the presence of [Fe(cp)2]BF4(cp =η5-C5H5) or FeCl3 gives the alkyne cluster derivatives [Ru6C(CO)15(µ3-η2-RCCR′)][R = R′= H (2), Me (3), Et (4), or Ph (5); R ≠ R′, H and Ph (6), Me and Ph (7)] as the respective major products at room temperature. Prolonged heating of the cluster [Ru6C(CO)15(µ3-η2-PhCCH)](6) in toluene over 3 d converts it into [Ru6C(CO)15(µ-H)(CCPh)](8), with hydride migration from the organo-fragment to a ruthenium metal centre. The structure of complexes (6) and (7) have been established by X-ray diffraction studies which show the alkyne ligands bonding to triangular ruthenium faces in a µ3-η2 mode.

[1]  Jack Lewis,et al.  Polyhedral rearrangements in undeca- and dodeca-nuclear Group 1B metal osmium clusters , 1989 .

[2]  Jack Lewis,et al.  The chemical activation of iron, ruthenium, and osmium carbonyl cluster anions using oxidative addition , 1988 .

[3]  Jack Lewis,et al.  The preparation, characterization and some reactions of [Ru3(CO)11(NCMe)] and [Ru3(CO)10(NCMe)2] , 1985 .

[4]  Jack Lewis,et al.  ortho-metallation reactions of variously substituted methylpyridines, quinoline, isoquinoline, diazines and 2,2′-bipyridine, with [Ru3(CO)10(NCMe)2] , 1985 .

[5]  P. Raithby,et al.  Synthesis of high nuclearity cluster alkynes under mild reaction conditions; the X-ray crystal structures of [Os6(CO)17(µ-H)(µ4-η-CCEt)], [Os6(CO)17(µ4-η2-HCCEt)], and [Os6(CO)16(µ3-η-MeCCEt)] , 1985 .

[6]  G. Somorjai.  Centenary Lecture. Molecular ingredients of heterogeneous catalysis , 1984 .

[7]  P. Braunstein,et al.  Alkyne-substituted homo- and heterometallic carbonyl clusters of the iron, cobalt and nickel triads , 1983 .

[8]  D. I. Stuart,et al.  An empirical method for correcting diffractometer data for absorption effects , 1983 .

[9]  J. Shapley,et al.  SYSTEMATIC AND EFFICIENT SYNTHESES OF RU6(CO)182-, RU6C(CO)162-, OS6(CO)182-, AND OS10C(CO)242-. ISOLATION AND CHARACTERIZATION OF OS6C(CO)17 , 1982 .

[10]  M. Mcpartlin,et al.  Metallation of the isopropenyl group by platinum(II): mechanism of formation of isomeric σ-allylic and σ-vinylic six-membered chelate rings. X-Ray structure of the σ-vinylic complex di-µ-acetato-bis-{[2-(o-diphenylarsinophenyl)propenyl–C′As]platinum(II)} , 1982 .

[11]  E. Muetterties.  The organometallic chemistry of metal surfaces , 1981 .

[12]  Robert C. Brady,et al.  Mechanism of the Fischer-Tropsch reaction. The chain propagation step , 1981 .

[13]  G. Ansell,et al.  Structure of 3-(16-?-bitropyl)-carbido--carbonyl-tridecacarbonyl-octahedro-hexaruthenium , 1980 .

[14]  M. Mcpartlin,et al.  An improved synthesis of the hexaruthenium carbido cluster Ru6C(CO)17; X-ray structure of the salt [Ph4As]2[Ru6C(CO)16] , 1980 .