TY - JOUR
T1 - Syntheses and Reactivity Studies of the Carbido-Alkylidyne Cluster Complexes LWRu4(μ5-C)(μ-CPh)(CO)12 and LWRu5(μ6-C)(μ-CPh)(CO)14, L = Cp and Cp*, Obtained from Reversible Scission of Acetylide Ligand
AU - Hwang, Shu-Fen
AU - Chi, Yun
AU - Chiang, Shun-Jean
AU - Peng, Shie-Ming
AU - Lee, Gene-Hsiang
PY - 2001/1/1
Y1 - 2001/1/1
N2 - Treatment of a 1:1 mixture of Ru3(CO)12 and the acetylide cluster LWRu2(CO)8(C2Ph) (1, L = Cp and Cp*) in hydrocarbon solvents afforded two carbido-alkylidyne cluster complexes, LWRu4(μ5-C)(CO)12(μ-CPh) (2) and LWRu5(μ6-C)(CO)14(μ-CPh) (3). Complexes 2 contain a square pyramidal cluster skeleton with a μ5-carbide and an accompanying bridging alkylidyne ligand, while WRu5 complexes 3 possess a distorted octahedral WRu5(μ6-C) framework. The transformation from 1 to 2 and 3 illustrates a reversible cleavage of an acetylide carbon−carbon bond induced by the cluster-building reaction. Moreover, the hydrogenation of complexes 2 and 3 was found to depend on the ancillary ligand on the W atom, showing selective formation of only two hydride complexes, CpWRu4(μ5-C)(μ-CPh)(μ-H)2(CO)11 (4) and Cp*WRu5(μ6-C)(μ-CPh)(μ-H)2(CO)13 (5), respectively. Single-crystal X-ray analysis on complex 4 indicated that the hydrides resided near the apical Ru atom, while the hydrides in complex 5 were associated with the unique W metal atom. Finally, treatment of 2 with thiophenol has led to formation of the wingtip-bridged butterfly complexes LWRu4(μ5-C)(μ-CPh)(μ-H)(μ-SPh)(CO)11 (7a, L = Cp; 7b, L = Cp*), in which the thiolate ligand is bonded to the Ru atoms separated by a nonbonding distance of 3.4186(8) Å.
AB - Treatment of a 1:1 mixture of Ru3(CO)12 and the acetylide cluster LWRu2(CO)8(C2Ph) (1, L = Cp and Cp*) in hydrocarbon solvents afforded two carbido-alkylidyne cluster complexes, LWRu4(μ5-C)(CO)12(μ-CPh) (2) and LWRu5(μ6-C)(CO)14(μ-CPh) (3). Complexes 2 contain a square pyramidal cluster skeleton with a μ5-carbide and an accompanying bridging alkylidyne ligand, while WRu5 complexes 3 possess a distorted octahedral WRu5(μ6-C) framework. The transformation from 1 to 2 and 3 illustrates a reversible cleavage of an acetylide carbon−carbon bond induced by the cluster-building reaction. Moreover, the hydrogenation of complexes 2 and 3 was found to depend on the ancillary ligand on the W atom, showing selective formation of only two hydride complexes, CpWRu4(μ5-C)(μ-CPh)(μ-H)2(CO)11 (4) and Cp*WRu5(μ6-C)(μ-CPh)(μ-H)2(CO)13 (5), respectively. Single-crystal X-ray analysis on complex 4 indicated that the hydrides resided near the apical Ru atom, while the hydrides in complex 5 were associated with the unique W metal atom. Finally, treatment of 2 with thiophenol has led to formation of the wingtip-bridged butterfly complexes LWRu4(μ5-C)(μ-CPh)(μ-H)(μ-SPh)(CO)11 (7a, L = Cp; 7b, L = Cp*), in which the thiolate ligand is bonded to the Ru atoms separated by a nonbonding distance of 3.4186(8) Å.
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U2 - 10.1021/om000801a
DO - 10.1021/om000801a
M3 - RGC 21 - Publication in refereed journal
SN - 0276-7333
VL - 20
SP - 215
EP - 223
JO - Organometallics
JF - Organometallics
IS - 1
ER -