Prototypical Phosphine Complexes of Antimony(III)

Complexes
of the generic formula [Cln(PR3)mSb](3–n)+ (n = 1, 2, 3, or 4 and m = 1 or 2) have been prepared featuring [ClSb]2+, [Cl2Sb]1+, Cl3Sb, or [Cl4Sb]1− as acceptors with one or two phosphine ligands
{PMe3, PPh3, PCy3 (Cy = C6H11)}. The solid-state structures of the complexes reveal
foundational features that define the coordination chemistry of a
lone pair bearing stibine acceptor site. The experimental observations
are interpreted with dispersion-corrected density functional theory
calculations to develop an understanding of the bonding and structural
diversity.

已制备得到通式为[Clₙ(PR₃)ₘSb]^((3−n)+)（n=1、2、3或4，m=1或2）的配合物，该类配合物以[ClSb]²+、[Cl₂Sb]+、Cl₃Sb或[Cl₄Sb]⁻作为受体，结合1或2个膦配体，包括三甲基膦（PMe3）、三苯基膦（PPh3）与三环己基膦（PCy3，其中Cy=C6H11）。该类配合物的固态结构揭示了含孤对电子的锑受体位点配位化学的核心特征。本研究通过色散校正密度泛函理论（density functional theory，DFT）计算对实验观测结果进行解析，以阐明其成键模式与结构多样性。