Reactions of the dinuclear ruthenium complex {(η5-C5H3)2(SiMe2) 2}Ru2(CO)4, featuring a doubly linked dicyclopentadienyl ligand

Maxim V. Ovchinnikov, David P. Klein, Ilia A. Guzei, Moon Gun Choi, Robert J. Angelici

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Abstract

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.

Original languageEnglish
Pages (from-to)617-627
Number of pages11
JournalOrganometallics
Volume21
Issue number4
DOIs
Publication statusPublished - 2002 Feb 18

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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