Iminophosphonamido-Supported Plumbylenes and Plumbyliumylidenes: Synthesis and Properties

A series of low-valent lead(II) species, i.e., plumbylenes and plumb­ylium­ylidenes supported by an N,N′-di-tert-butyl­imino­phosphon­amide ligand, have been synthesized. Chloroplumbylene [Ph₂P(N^tBu)₂PbCl] (1) was readily prepared by the reaction of the corresponding lithium iminophos­phonamide and PbCl₂ in THF. The substitution reaction of 1 with KN(SiMe₃)₂ in THF afforded the corresponding aminoplumbylene [Ph₂P(N^tBu)₂PbN(SiMe₃)₂] (2) in the form of colorless crystals. The structures of these plumbylenes in the solid state and in solution were exhaustively characterized using multinuclear NMR spectroscopy and X-ray diffraction analysis. In the crystalline state, 1 adopts a nearly linear polymeric structure in the direction of the c axis via Pb–Cl bonds, with alternating four-membered PbN₂P rings. The chloride-abstraction reaction of 1 using Na[B(C₆F₅)₄] in fluorobenzene proceeded efficiently at ambient temperature to furnish plumb­yliumylidene [Ph₂P(N^tBu)₂Pb:]⁺ (3⁺), which was isolated as the air-sensitive yellow borate salt 3[B(C₆F₅)₄]. Plumb­yliumylidene 3[B(C₆F₅)₄] acts as a Lewis acid catalyst for the hydroboration of benzophenone and benzaldehyde at catalyst loadings of as low as 0.1 mol % under ambient conditions. Furthermore, the details of the reaction mechanism are discussed on the basis of the results of DFT calculations.