Kinetic Destabilization of Metal–Metal Single Bonds: Isolation of a Pentacoordinate Manganese(0) Monoradical

Abstract

AbstractThe 17e− monoradical [Mn(CO)5] is widely recognized as an unstable organometallic transient and is known to dimerize rapidly with the formation of a MnMn single bond. As a result of this instability, isolable analogues of [Mn(CO)5] have remained elusive. Herein, we show that two sterically encumbering isocyanide ligands can destabilize the MnMn bond leading to the formation of the isolable, manganese(0) monoradical [Mn(CO)3(CNArDipp2)2] (ArDipp2=2,6‐(2,6‐(iPr)2C6H3)2C6H3). The persistence of [Mn(CO)3(CNArDipp2)2] has allowed for new insights into nitrosoarene spin‐trapping studies of [Mn(CO)5].