Crystal structures of three complexes of zinc chloride with tri-tert-butyl-phosphane

Aaron D Finke; Danielle L Gray; Jeffrey S Moore

doi:10.1107/S2056989015023373

Crystal structures of three complexes of zinc chloride with tri-tert-butyl-phosphane

Acta Crystallogr E Crystallogr Commun. 2016 Jan 1;72(Pt 1):35-9. doi: 10.1107/S2056989015023373.

Authors

Aaron D Finke¹, Danielle L Gray², Jeffrey S Moore³

Affiliations

¹ Swiss Light Source, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland.
² University of Illinois, School of Chemical Sciences, Box 59-1, 505 South Mathews Avenue, Urbana, Illinois 61801, USA.
³ University of Illinois, School of Chemical Sciences, Box 55-5, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.

Abstract

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.

Keywords: Lewis base; crystal structure; tri-tert-butylphosphane; zinc chloride.