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Two-state reactivity as a new concept in organometallic chemistry
D Schröder1, S Shaik, H Schwarz
1Institut für Organische Chemie der Technischen Universität Berlin, Strasse des 17 Juni 135, D-10623 Berlin, Germany.
Abstract:
It is proposed that spin-crossing effects can dramatically affect reaction mechanisms, rate constants, branching ratios, and temperature behaviors of organometallic transformations. This phenomenon is termed two-state reactivity (TSR) and involves participation of spin inversion in the rate-determining step. While the present analysis is based on studies of transition metals under idealized conditions, several recent reports imply that TSR is by no means confined to the gas phase. In fact, participation of more than a single spin surface in the reaction pathways is proposed as a key feature in organometallic chemistry.