The agostic interaction between a transition metal and a C-H bond is important in organometallic catalysis. These 3-center-2-electron bonds can be problematic in Pd (or Ni) catalyzed alkyl cross coupling, where Pd(II)-alkyl intermediates containing agostic interactions can undergo facile �-elimination.           We use density functional theory (DFT) to model Pd catalyzed alkyl cross coupling, including undesirable �-hydride eliminations. The selectivity of the desired product is strongly influenced by the ligands and nucleophiles interaction with coordinatively unsaturated Pd(II) intermediates. The strength of the agostic interactions, and thus the rate of �-elimination, depends on the ancillary ligands in Pd(II). We systematically benchmark several DFT approximations against high-level ab initio calculations for model agostic complexes. We then use the most accurate methods to explore how agostic interactions depend on ligand donor-acceptor properties. Our results provide a better understanding of controlling �-elimination via proposed �design rules� on ligand choices.

Agostic interactions in transition metal d<sup>8</sup> complexes: Critical role of ancillary ligands on the strength of the bond

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Agostic interactions in transition metal d8 complexes: Critical role of ancillary ligands on the strength of the bond

Agostic interactions in transition metal d⁸ complexes: Critical role of ancillary ligands on the strength of the bond