Stepwise Formation of Heterometallic Cluster Compounds (C₅Me₅)WRu₅(μ₆-C)(μ-CCH₂Ph)(μ-H)₂(CO)₁₃and (C₅Me₅)WRu₅(μ₄-C)(μ₃-CCH₂Ph)(μ-H)₄(CO)₁₂from Ru₅(μ₅-C)(CO)₁₅. Reactivity Studies of Carbido Clusters Bearing Acetylide Ligands

Abstract

Treatment of the carbido cluster Ru5(μ5-C)(CO)15 with Me3NO followed by addition of the tungsten acetylide complexes LW(CO)3(CCPh) (L = Cp, C5Me5) affords the two heterometallic cluster complexes LWRu5(μ5-C)(CCPh)(CO)15 (1a, L = Cp; 1b, L = C5Me5) and LWRu5(μ5-C)(CCPh)(CO)13 (2a, L = Cp; 2b, L = C5Me5). Thermolysis of 1 results in the irreversible formation of 2. The reactivity of 2 was studied. Thus, hydrogenation of 2b furnishes the two cluster compounds (C5Me5)WRu5(μ6-C)(μ-CCH2Ph)(μ-H)2(CO)13 (3) and (C5Me5)WRu5(μ4-C)(μ3-CCH2Ph)(μ-H)4(CO)12 (4), generated via 1,1-addition of H2 to the ligated acetylide and concurrent formation of two or four bridging hydrides. Treatment of 3 with CO gives the octahedral cluster (C5Me5)WRu5(μ6-C)(μ-CCH2Ph)(CO)14 (5). The spectral and structural properties of all species are presented and discussed.

Syntheses and Reactivity Studies of the Carbido-Alkylidyne Cluster Complexes LWRu4(μ5-C)(μ-CPh)(CO)12and LWRu5(μ6-C)(μ-CPh)(CO)14, L = Cp and Cp*, Obtained from Reversible Scission of Acetylide Ligand

“…The identification of 5 was achieved using spectroscopic methods, of which the 1 H NMR spectrum showed a high-field signal at δ -16.72 (J WC ) 77 Hz) corresponding to two W-H-Ru bridging hydride ligands. Moreover, the IR spectrum exhibits a ν(CO) pattern that is almost identical to that of the previously reported hydride complex Cp*WRu 5 (µ 6 -C)(µ-CCH 2 Ph)(µ-H) 2 (CO) 13 (6, Chart 1), 17 obtained from direct hydrogenation of the carbido-acetylide complex Cp*WRu 5 (µ 5 -C)(CCPh)(CO) 13 .…”

Synthesis of the First Cluster Complexes Bearing Three Quadruply Bridging CO Ligands: X-ray Crystal Structure of [C5H3(SiMe3)2]WRu6(μ3-H)- (CO)18

“…Again, the hydride ligands are located, and they span the newly formed W−Ru(1) edge, the Ru(2)−Ru(3) edge, and the Ru(2)−Ru(4)-Ru(5) face, respectively. These assignments are fully consistent with the 1 H NMR data which exhibit three signals at δ −14.14 ( J WH = 84.8 Hz), −14.70, and −20.71; the last one is obviously due to the face-bridging hydride because of the large distinction in chemical shift 2 Molecular structure of 2 and the atomic numbering scheme; the methyl groups of the trimethylsilyl substituents were omitted for clarity.…”