Stepwise Expansion of Pd Chains from Binuclear Palladium(I) Complexes Supported by Tetraphosphine Ligands.

Abstract

Reaction of [Pd2(XylNC)6]X2 (X = PF6, BF4) with a linear tetraphosphine, meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), afforded binuclear Pd(I) complexes, [Pd2(μ-dpmppm)2]X2 ([2]X2), through an asymmetric dipalladium complex, [Pd2(μ-dpmppm)(XylNC)3](2+) ([1](2+)). Complex [2](2+) readily reacted with [Pd(0)(dba)2] (2 equiv) and an excess of isocyanide, RNC (R = 2,6-xylyl (Xyl), tert-butyl ((t)Bu)), to generate an equilibrium mixture of [Pd4(μ-dpmppm)2(RNC)2](2+) ([3'](2+)) + RNC ⇄ [Pd4(μ-dpmppm)2(RNC)3](2+) ([3](2+)), from which [Pd4(μ-dpmppm)2(XylNC)3](2+) ([3a](2+)) and [Pd4(μ-dpmppm)2((t)BuNC)2](2+) ([3b'](2+)) were isolated. Variable-temperature UV-vis and (31)P{(1)H} and (1)H NMR spectroscopic studies on the equilibrium mixtures demonstrated that the tetrapalladium complexes are quite fluxional in the solution state: the symmetric Pd4 complex [3b'](2+) predominantly existed at higher temperatures (>0 °C), and the equilibrium shifted to the asymmetric Pd4 complex [3b](2+) at a low temperature (∼-30 °C). The binding constants were determined by UV-vis titration at 20 °C and revealed that XylNC is of higher affinity to the Pd4 core than (t)BuNC. In addition, both isocyanides exhibited higher affinity to the electron deficient [Pd4(μ-dpmppmF2)2(RNC)2](2+) ([3F'](2+)) than to [Pd4(μ-dpmppm)2(RNC)2](2+) ([3'](2+)) (dpmppmF2 = meso-bis[{di(3,5-difluorophenyl)phosphinomethyl}phenylphosphino]methane). When [2]X2 was treated with [Pd(0)(dba)2] (2 equiv) in the absence of RNC in acetonitrile, linearly ordered octapalladium chains, [Pd8(μ-dpmppm)4(CH3CN)2]X4 ([4]X4: X = PF6, BF4), were generated through a coupling of two {Pd4(μ-dpmppm)2}(2+) fragments. Complex [2](2+) was also proven to be a good precursor for Pd2M2 mixed-metal complexes, yielding [Pd2Cl(Cp*MCl) (Cp*MCl2)(μ-dpmppm)2](2+) (M = Rh ([5](2+)), Ir ([6](2+)), and [Au2Pd2Cl2(dpmppm-H)2](2+) ([7](2+)) by treatment with [Cp*MCl2]2 and [AuCl(PPh3)], respectively. Complex [7](2+) contains an unprecedented PC(sp(3))P pincer ligand with a PCPCPCP backbone, dpmppm-H of deprotonated dpmppm. The present results demonstrated that the binuclear Pd(I) complex [2](2+) was a quite useful starting material to extend the palladium chains and to construct Pd-involved heteromultinuclear systems.