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Thermochemistry and molecular structure of a remarkable agostic interaction in a heterobifunctional ruthenium-boron complex.

ABSTRACT: A boron-pendant ruthenium species forms a unique agostic methyl bridge between the boron and ruthenium atoms in the presence of a ligating solvent, acetonitrile. NMR inversion-recovery experiments enabled the activation and equilibrium thermochemistry for formation of the agostic bridge to be measured. The mechanism for bridge formation involves displacement of an acetonitrile ligand; thus, this is a rare example of a case where an agostic C-H ligand competitively displaces another tightly binding ligand from a coordinatively saturated complex. Characterization of this complex gives unique insights into the development of C-H activation catalysis based on this ligand-metal bifunctional motif.

SUBMITTER: Conley BL

PROVIDER: S-EPMC2846719 | biostudies-literature | 2010 Feb

REPOSITORIES: biostudies-literature

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Thermochemistry and molecular structure of a remarkable agostic interaction in a heterobifunctional ruthenium-boron complex.

Conley Brian L BL Williams Travis J TJ

Journal of the American Chemical Society 20100201 6

A boron-pendant ruthenium species forms a unique agostic methyl bridge between the boron and ruthenium atoms in the presence of a ligating solvent, acetonitrile. NMR inversion-recovery experiments enabled the activation and equilibrium thermochemistry for formation of the agostic bridge to be measured. The mechanism for bridge formation involves displacement of an acetonitrile ligand; thus, this is a rare example of a case where an agostic C-H ligand competitively displaces another tightly bindi ...[more]

PMID: 20088526

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