Synthesis and characterization of novel oxo-centered phosphanylzincates of potassium and cesium with a central Zn6O2P4 double-heterocubane cage

Matthias Westerhausen; Gerhard Sapelza; Helmar Görls; Peter Mayer

doi:10.1021/ic0515195

Synthesis and characterization of novel oxo-centered phosphanylzincates of potassium and cesium with a central Zn6O2P4 double-heterocubane cage

Inorg Chem. 2006 Jan 9;45(1):409-14. doi: 10.1021/ic0515195.

Authors

Matthias Westerhausen¹, Gerhard Sapelza, Helmar Görls, Peter Mayer

Affiliation

¹ Friedrich-Schiller-Universität Jena, Institute of Inorganic and Analytical Chemistry, Germany. [email protected]

PMID: 16390082
DOI: 10.1021/ic0515195

Abstract

The hydrolysis reaction of K(2)(MeZn)(2)(PSitBu(3))(2) in THF/toluene solution yields the [(MeZn)(4)Zn(2)(mu(3)-PSitBu(3))(4)(mu(4)-O)(2)](4-) anions independent of the applied stoichiometry. If the applied molar ratio resembles the composition of the anion, [(thf)K](2)[(eta(6)-toluene)K](2)[(MeZn)(4)Zn(2)(mu(3)-PSitBu(3))(4)(mu(4)-O)(2)] (1) crystallizes from a mixture of THF and toluene. In the case with less water, a phosphanediylzincate moiety is bonded to this anion, and [Zn(PSitBu(3))(2)K(4)(thf)(6)](2)[(MeZn)(4)Zn(2)(mu(3)-PSitBu(3))(4)(mu(4)-O)(2)] (2) crystallizes. However, again the major product is 1. The same anion is also observed with larger and softer cations, and [(thf)(3)Cs(2)](2)[(MeZn)(4)Zn(2)(mu(3)-PSitBu(3))(4)(mu(4)-O)(2)] (3) is obtained if the cesium zincate is used in this reaction. In all of these compounds, the anion is a slightly distorted Zn(6)O(2)P(4) double-heterocubane cage with a central Zn(2)O(2) ring having Zn-O bond lengths of approximately 207 pm.