Carbamoyl Complexes of Divalent Tungsten, Molybdenum, and Iron and the Unexpected Formation of an Aminomethylidyne Complex

Abstract

Sequential treatment of [M(CO)6] (M = W, Mo, but not Cr) with 1 equiv of LiNiPr2, iodine, and PPh3 provides [M(η2-OCNiPr2)I(CO)3(PPh3)], which serve as precursors for a wide range of bidentate carbamoyl complexes; however, if for M = W, an excess of LiNiPr2 is employed, the aminomethylidyne complex [W(⋮CNiPr2)I(CO)3(PPh3)] is also obtained.