Manganese and iron PCP pincer complexes – the influence of sterics on structure and reactivity

Abstract

The syntheses of various manganese and iron PCP pincer complexes via a solvothermal oxidative addition methodology is described. Upon reacting [Mn₂(CO)₁₀] with the ligands (P(C–Br)P^CH₂-iPr) (1a) and (P(C–Br)P^O-iPr) (1b), Mn(I) PCP pincer complexes [Mn(PCP^CH₂-iPr)(CO)₃] (2a) and [Mn(-PCP^O-iPr)(CO)₃] (2b) were obtained. Protonation of 2a with HBF₄·Et₂O led to the formation of [Mn(κ³P,CH,P-P(CH)P^CH₂-iPr)(CO)₃]BF₄ (3) featuring an η²-C_aryl–H agostic bond. The solvothermal reaction of 1a with [Fe₂(CO)₉] afforded the Fe(II) PCP pincer complex [Fe(PCP^CH₂-iPr)(CO)₂Br] (4). Treatment of 4 with Li[HBEt₃] afforded the Fe(I) complex [Fe(PCP^CH₂-iPr)(CO)₂] (5a). When using the sterically more demanding ligands (P(C–Br)P^CH₂-tBu) (1c) and (P(C–Br)P^O-tBu)(1d) striking differences in reactivity were observed. While neither 1c nor 1d showed any reactivity towards [Mn₂(CO)₁₀], the reaction with [Fe₂(CO)₉] and [Fe(CO)₅] led to the formation of the Fe(I) complexes [Fe(PCP^CH₂-tBu)(CO)₂] (5b) and [Fe(PCP^O-tBu)(CO)₂] (5c). X-ray structures of representative complexes are provided.