title: Reactivity of divalent germanium alkoxide complexes is in sharp contrast to the heavier tin and lead analogues.
abstract: The chemistry of β-diketiminate germanium alkoxide complexes has been examined and shown to be in sharp contrast to its heavier congeners. For instance, (BDI)GeOR (BDI = [{N(2,6-(i)Pr(2)C(6)H(3))C(Me)}(2)CH], R = (i)Pr, (s)Bu, (t)Bu) does not react with carbon dioxide to form a metal carbonate complex. Addition of aliphatic electrophiles, such as methyl iodide or methyl triflate, results in the net oxidative addition to the germanium, giving cationic tetravalent germanium complexes, [(BDI)Ge(Me)OR][X] (X = I, OTf). An examination of the contrasting reactivities of the alkoxide ligand and the germanium loan pair with Lewis acids yielded the unusual germanium(II)-copper(I) adduct, {μ(2)-Cu(2)I(2)}[(BDI)GeO(t)Bu](2). This complex not only displays a rare example of a divalent Ge-Cu bond, but is the first example in which a planar Cu(2)I(2) diamond core possesses a three-coordinate copper bound to another metal center.
authors.affiliation: Department of Chemistry, University of Sussex, Falmer, Brighton BN1 9QJ, United Kingdom.
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Ferro
authors.forename: Peter B
authors.initials: PB
authors.lastname: Hitchcock
authors.forename: Martyn P
authors.initials: MP
authors.lastname: Coles
authors.forename: J Robin
authors.initials: JR
authors.lastname: Fulton