Coordination Networks Derived From Germanium(ii) Thioether Macrocyclic Complexes-the First Authenticated Chalcogenoether Complexes Of Ge(ii)

摘要

Exocyclic coordination of macrocyclic thioethers to germanium(II) halides leads to infinite chains (with weak Ge… X bridges between the chains) or sheet structures containing distorted octahedral Ge(II) with [S_2X_2 + X_2 ]coordination and bridging thiacrowns.rnAlthough the chemistry of germanium with neutral, soft donor ligands has been extended significantly recently, this work has focused on tetravalent germanium, yielding the first [GeF_4(dipho-sphine)] and [GeF_4(dithioether)] complexes. Investigations of the lower valent Ge(II) ion have focused mainly on germylenes (Ge analogues of carbenes) and for applications in organic chemistry. Further interest in complexes of Ge(II) arises from the presence of a lone pair of electrons which is expected to have significant stereo-chemical consequences. However, reports of the coordination chemistry of Ge(II) with neutral ligands are few-structural data available are for [GeCl_2(dioxan)], the very unstable [GeCl_2(thf)_2] and a single diphosphine complex, [GeCl_2{Ph_2P(CH_2)_2PPh_2}]-each of which contains Ge(II) in a highly distorted tetrahedral environment.