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Reactivity of Divalent Germanium Alkoxide Complexes Is in Sharp Contrast to the Heavier Tin and Lead Analogues

Reactivity of Divalent Germanium Alkoxide Complexes Is in Sharp Contrast to the Heavier Tin and Lead Analogues

Lorenzo Ferro, Peter B Hitchcock, Martyn P Coles, J Robin Fulton

Inorg Chem. 2012 Feb 6;51(3):1544-51.

PMID: 22242862

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP13573085	Germanium(II) iodide		13573-08-5	Price

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