Heterobimetallic Activation of Dioxygen: Characterization and Reactivity of Novel Cu(I)−Ge(II) Complexes

Reaction of the known germylene Ge[N(SiMe3)2]2 and a new heterocyclic variant Ge[(NMes)2(CH)2] with [LMe2Cu]2
(LMe2 = the β-diketiminate derived from 2-(2,6-dimethylphenyl)amino-4-(2,6-dimethylphenyl)imino-2-pentene) yielded
novel Cu(I)−Ge(II) complexes LMe2Cu−Ge[(NMes)2(CH)2] (1a) and LMe2Cu−Ge[N(SiMe3)2]2 (1b), which were
characterized by spectroscopy and X-ray crystallography. The lability of the Cu(I)−Ge(II) bond in 1a and b was
probed by studies of their reactivity with benzil, PPh3, and a N-heterocyclic carbene (NHC). Notably, both complexes
are cleaved rapidly by PPh3 and the NHC to yield stable Cu(I) adducts (characterized by X-ray diffraction) and the
free germylene. In addition, the complexes are highly reactive with O2 and exhibit chemistry which depends on the
bound germylene. Thus, oxygenation of 1a results in scission and formation of thermally unstable LMe2CuO2, which
subsequently decays to [(LMe2Cu)2(μ-O)2], while 1b yields LMe2Cu(μ-O)2Ge[N(SiMe3)2]2, a novel heterobimetallic
intermediate having a [CuIII(μ-O)2GeIV]3+ core. The isolation of the latter species by direct oxygenation of a Cu(I)−Ge(II) precursor represents a new route to heterobimetallic oxidants comprising copper.