✍ Scribed by Farman Ullah; Olaf Kühl; Gabor Bajor; Tamas Veszprémi; Peter G. Jones; Joachim Heinicke
No coin nor oath required. For personal study only.
The five‐membered N‐heterocyclic germylenes (NHGe) 1a–3a, with or without benzo or naphtho anellation, react with [Mo(CO)~3~(cht)] (cht = 1,3,5‐cycloheptatriene) to form the__fac__‐[(NHGe)~3~Mo(CO)~3~] complexes 1b–3b. Similarly, [Ni(bnNHGe)~4~] was obtained from the benzo‐anellated germylene (bnNHGe) and Ni(1,5‐cod)~2~; attempts to synthesize less electron‐rich complexes with mono‐ or divalent transition metals failed. The CO valence vibrations in the IR spectra of 1b–3b, together with their short Ge^II^–Mo bonds (as determined by X‐ray crystallography), hint at the weak donor and good π‐acceptor properties of the ligands. Quantum chemical studies on the benzo‐anellated germylene, which are supported by the good correlation between calculated and experimental (PES) orbital ionization potentials, confirm this proposal in terms of the low energy of the Ge lone electron pair and two higher π‐MOs. The slight folding about the C–C bridging and N···N axes observed for the benzo‐anellated (NHGe)molybdenum and ‐nickel complexes by X‐ray structure analyses, may be due to packing effects. Quantum chemical calculations on slightly bent (for dineopentyl substitution in the gas phase) and planar bnNHGe complexes show that the energy differences between the two are very small.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
📜 SIMILAR VOLUMES
## Abstract For Abstract see ChemInform Abstract in Full Text.
N-Picolyl polyurethanes (PUPY) were synthesized by nucleophilic substitution. The blends of these polyurethanes with various of transition metal chlorides [cobalt(II), nickel(II), and copper(II)] were studied by spectroscopic and thermal analysis. Ultraviolet-visible and infrared spectroscopic evide