To synthesize complexes with thorium–phosphorus multiple-bond character, reactions of (C₅Me₅)₂Th[P(H)Mes]₂ with monovalent alkali-metal bases, MN(SiMe₃)₂, as well as CuMes, have been investigated. The results with MN(SiMe₃)₂ are phosphinidiide complexes of the form {(C₅Me₅)₂Th[μ₂-P(Mes)][μ₂-P(H)Mes]M(L)_n}₂ (M = Na, n = 0; M = K, L = THF, n = 1; M = Rb, L = THF, n = 1; M = Cs, L = Et₂O, n = 1). With CuMes, the product is a Th₂Cu₃P₅ heterometallic structure, {(C₅Me₅)₂Th[(μ₂-P(H)Mes)P(Mes)]Cu}₂Cu[μ₂-P(H)Mes]. All complexes have been characterized using heteronuclear NMR and IR spectroscopy, density functional theory calculations, and their solid-state structure identified by X-ray crystallography. We also report the structure of {(C₅Me₅)₂Th[(μ₂-As(H)Mes)As(Mes)]Cu}₂Cu[μ₂-As(H)Mes] obtained from (C₅Me₅)₂Th[As(H)Mes]₂ with CuMes.

中文翻译：

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异金属磷化钍配合物的结构、光谱和计算分析

为了合成具有钍-磷多键特性的配合物，(C ₅ Me ₅ ) ₂ Th[P(H)Mes] ₂与一价碱金属碱、MN(SiMe ₃ ) ₂以及CuMes的反应具有被调查。MN(SiMe ₃ ) _{2 的结果}是 {(C ₅ Me ₅ ) ₂ Th[μ ₂ -P(Mes)][μ ₂ -P(H)Mes]M(L) _n } ₂ (M = Na, n = 0; M = K, L = THF, n = 1; M = Rb, L = THF, n= 1; M = Cs，L = Et ₂ O，n = 1)。使用CuMes，产物为Th ₂ Cu ₃ P ₅异金属结构，{(C ₅ Me ₅ ) ₂ Th[(μ ₂ -P(H)Mes)P(Mes)]Cu} ₂ Cu[μ ₂ -P （H）我]。所有配合物都已使用异核 NMR 和 IR 光谱、密度泛函理论计算以及通过 X 射线晶体学确定的固态结构进行了表征。我们还报告了 {(C ₅ Me ₅ ) ₂ Th[(μ ₂ -As(H)Mes)As(Mes)]Cu} ₂ Cu[μ ₂-As(H)Mes] 从 (C ₅ Me ₅ ) ₂ Th[As(H)Mes] ₂与 CuMes 获得。