Finke Aaron D, Gray Danielle L, Moore Jeffrey S
Swiss Light Source, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland.
University of Illinois, School of Chemical Sciences, Box 59-1, 505 South Mathews Avenue, Urbana, Illinois 61801, USA.
Acta Crystallogr E Crystallogr Commun. 2016 Jan 1;72(Pt 1):35-9. doi: 10.1107/S2056989015023373.
Under anhydrous conditions and in the absence of a Lewis-base solvent, a zinc chloride complex with tri-tert-butyl-phosphane as the μ-bridged dimer is formed, viz. di-μ-chlorido-bis-[chlorido-bis-(tri-tert-butyl-phosphane)zinc], [ZnCl4(C12H27P)2], (1), which features a nearly square-shaped (ZnCl)2 cyclic core and whose Cl atoms inter-act weakly with C-H groups on the phosphane ligand. In the presence of THF, monomeric di-chlorido-(tetra-hydro-furan-κO)(tri-tert-butyl-phosphane-κP)zinc, [ZnCl2(C4H8O)(C12H27P)] or [P(tBu3)(THF)ZnCl2], (2), is formed. This slightly distorted tetra-hedral Zn complex has weak C-H⋯Cl inter-actions between the Cl atoms and phosphane and THF C-H groups. Under ambient conditions, the hydrolysed complex tri-tert-butyl-phospho-nium aqua-tri-chlorido-zincate 1,2-di-chloro-ethane monosolvate, (C12H28P)[ZnCl3(H2O)]·C2H4Cl2 or HPtBu3 (H2O)ZnCl3·C2H4Cl2, (3), is formed. This complex forms chains of (H2O)ZnCl3 anions from hydrogen-bonding inter-actions between the water H atoms and Cl atoms that propagate along the b axis.
在无水条件下且不存在路易斯碱溶剂时，会形成一种以三叔丁基膦作为μ-桥联二聚体的氯化锌配合物，即二-μ-氯代-双-[氯代-双-(三叔丁基膦)锌]，[ZnCl₄(C₁₂H₂₇P)₂]，(1)，它具有近乎方形的(ZnCl)₂环状核心，且其Cl原子与膦配体上的C-H基团存在弱相互作用。在四氢呋喃（THF）存在的情况下，会形成单体二氯代-(四氢呋喃-κO)(三叔丁基膦-κP)锌，[ZnCl₂(C₄H₈O)(C₁₂H₂₇P)] 或 [P(tBu₃)(THF)ZnCl₂]，(2)。这种略微扭曲的四面体锌配合物在Cl原子与膦以及THF的C-H基团之间存在弱的C-H⋯Cl相互作用。在环境条件下，会形成水解后的配合物三叔丁基鏻水合三氯代锌酸盐1,2-二氯乙烷单溶剂化物，(C₁₂H₂₈P)[ZnCl₃(H₂O)]·C₂H₄Cl₂ 或 HPtBu₃ (H₂O)ZnCl₃·C₂H₄Cl₂，(3)。该配合物通过水分子H原子与Cl原子之间的氢键相互作用形成(H₂O)ZnCl₃阴离子链，这些链沿b轴延伸。
