3H-Benzophosphepine Complexes:  Versatile Phosphinidene Precursors

The synthesis of a variety of benzophosphepine complexes [R = Ph, t-Bu, Me; MLn = W(CO)5, Mo(CO)5, Cr(CO)5, Mn(CO)2Cp] by two successive hydrophosphinations of 1,2-diethynylbenzene is discussed in detail. The first hydrophosphination step proceeds at ambient temperature without additional promoters, and subsequent addition of base allows full conversion to benzophosphepines. Novel benzeno-1,4-diphosphinanes were isolated as side products. The benzophosphepine complexes themselves serve as convenient phosphinidene precursors at elevated, substituent-dependent temperatures (>55 °C). Kinetic and computational analyses support the proposal that the phosphepine−phosphanorcaradiene isomerization is the rate-determining step. In the absence of substrate, addition of the transient phosphinidene to another benzophosphepine molecule is observed, and addition to 1,2-diethynylbenzene furnishes a delicate bidentate diphosphirene complex.