Breaking bonds and breaking rules: inert-bond activation by [(iPr3P)Ni]5H4 and catalytic stereospecific norbornene dimerization

Abstract

The facile carbon atom abstraction reaction by [(ⁱPr₃P)Ni]₅H₆ (1) with various terminal alkenes to give [(ⁱPr₃P)Ni]₅H₄(μ₅-C) (2) occurs via a common highly reactive intermediate [(ⁱPr₃P)Ni]₅H₄ (3), which was isolated by the reaction of 1 with norbornene. Temperature dependent ¹H and ³¹P{¹H} NMR chemical shifts of 3 are consistent with a thermally populated triplet excited state only 2 kcal mol⁻¹ higher energy than the diamagnetic ground state. Complex 3 catalyzes the dimerization of norbornene to stereoselectively provide exclusively (Z) anti-(bis-2,2'-norbornylidene).