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

摘要

The 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)] (Ar-Dipp2 = 2,6-(2,6-(iPr)(2)C6H3)(2)C6H3). The persistence of [Mn(CO)(3)(CNArDipp2)(2)] has allowed for new insights into nitrosoarene spin- trapping studies of [Mn(CO)(5)].