TY - JOUR
T1 - Reactions of the dinuclear ruthenium complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4, featuring a doubly linked dicyclopentadienyl ligand
AU - Ovchinnikov, Maxim V.
AU - Klein, David P.
AU - Guzei, Ilia A.
AU - Choi, Moon Gun
AU - Angelici, Robert J.
PY - 2002/2/18
Y1 - 2002/2/18
N2 - The complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4 (1), which features the doubly linked dicyclopentadienyl ligand (η5-C5H3)2(SiMe2) 2, reacts with phosphines (PMe3, PCy3, PPh3) to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)(μ-CO)2(PR3) (2a-c), with halogens X2 (X = Cl, Br, I) to give the Ru-Ru-cleaved products {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(X)2 (3a-c), with X2 and AgTfO to give [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-X)]+TfO- (X = Cl, Br, I; 4a-c), and with SnCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-SnCl2) (5), resulting from the insertion of SnCl2 into the Ru-Ru bond. Reduction of 1 with Na/Hg generates [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4]2- (6), which reacts with (η5-C5H5)2TiCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4{μ-Ti(η5-C5 H5)2} (7). Ultraviolet photolysis of 1 with diphenylacetylene and phenylacetylene yields a series of five dinuclear Ru complexes (8-10, 12, 13) containing one or two bridging acetylene units. The rigidity of the doubly linked (η5-C5H3)2(SiMe2) 2 ligand substantially influences the reactivity and structures of the complexes. Molecular structures of 1, 2a, 3c, 5, 9, 10, and 12 as determined by X-ray diffraction studies are also presented.
AB - The complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4 (1), which features the doubly linked dicyclopentadienyl ligand (η5-C5H3)2(SiMe2) 2, reacts with phosphines (PMe3, PCy3, PPh3) to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)(μ-CO)2(PR3) (2a-c), with halogens X2 (X = Cl, Br, I) to give the Ru-Ru-cleaved products {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(X)2 (3a-c), with X2 and AgTfO to give [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-X)]+TfO- (X = Cl, Br, I; 4a-c), and with SnCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4(μ-SnCl2) (5), resulting from the insertion of SnCl2 into the Ru-Ru bond. Reduction of 1 with Na/Hg generates [{(η5-C5H3)2(SiMe2) 2}Ru2(CO)4]2- (6), which reacts with (η5-C5H5)2TiCl2 to give {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4{μ-Ti(η5-C5 H5)2} (7). Ultraviolet photolysis of 1 with diphenylacetylene and phenylacetylene yields a series of five dinuclear Ru complexes (8-10, 12, 13) containing one or two bridging acetylene units. The rigidity of the doubly linked (η5-C5H3)2(SiMe2) 2 ligand substantially influences the reactivity and structures of the complexes. Molecular structures of 1, 2a, 3c, 5, 9, 10, and 12 as determined by X-ray diffraction studies are also presented.
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U2 - 10.1021/om010674y
DO - 10.1021/om010674y
M3 - Article
AN - SCOPUS:0038157269
SN - 0276-7333
VL - 21
SP - 617
EP - 627
JO - Organometallics
JF - Organometallics
IS - 4
ER -