Tetra-kis(di-cyclo-hexyl-amido)-zirconium(IV).

Nils Frerichs,Marc Schmidtmann,Rüdiger Beckhaus

doi:10.1107/s2414314620011451

Abstract

The reaction of ZrCl4 with three equivalents of LiNCy2 (Cy is cyclo-hex-yl) resulted in the formation of tris-(di-cyclo-hexyl-amido)-zirconium chloride and the title compound, [Zr(C12H22N)4]. The latter is isotypic with its cerium(IV) analogue and crystallizes with three independent mol-ecules in the asymmetric unit. One mol-ecule is located about a twofold rotation axis, and the other two on fourfold inversion axes. In each mol-ecule, the ZrIV atom has a distorted tetra-hedral coordination environment. The crystal under investigation was twinned by inversion in a 1:1 ratio.

Highlights

The reaction of ZrCl4 with three equivalents of LiNCy2 (Cy is cyclohexyl) resulted in the formation of tris(dicyclohexylamido)zirconium chloride and the title compound, [Zr(C12H22N)4]
One molecule is located about a twofold rotation axis, and the other two on fourfold inversion axes
Tetrakis(dialkylamido)zirconium(IV) compounds are commonly known as precursors of a variety of more complex zirconium-containing compounds (Diamond et al, 1995, 1996)

Summary

Structure description

Amido complexes of group 4 metals play an important role in synthetic chemistry. They are widely used as catalysts in hydroaminoalkylation reactions (Roesky et al, 2009) or in the catalysis of olefin polymerization reactions (Shafir & Arnold, 2001; Motolko et al, 2017). Dicyclohexylamido complexes of group 4 metals show close contacts between the central metal cation and the carbon atom of the CH group of one dicyclohexylamido ligand, which is an indicator for attractive agostic interactions (Duan et al, 1997; Adler et al, 2014b). The understanding of these interactions is very important (Scherer et al, 2010) because they are considered to be intermediates in C—H bond-activation processes. [Zr(C12H22N)4] 812.44 Tetragonal, P4 100 21.0321 (7), 10.2412 (5) 4530.2 (4) 4 Mo K 0.28 0.15 Â 0.11 Â 0.07

Data collection Diffractometer Absorption correction

Bruker Photon III CPAD diffractometer

Special details