Synthesis and Reaction of Monomeric Germanium(II) and Lead(II) Dimethylamide and the Synthesis of Germanium(II) Hydrazide by Clevage of one N−H bond of Hydrazine

The β-diketiminate substituted germanium(II) and lead(II) dimethylamides, LGeNMe2 (1) and LPbNMe2 (2), [L = CH{(CMe)2(2,6-iPr2C6H3N)2}] have been synthesized by the reaction of LiNMe2 with LGeCl and LPbCl respectively. Reaction of compound 1 with an equivalent amount of elemental sulfur leads to the germanium analogue of thioamide, LGe(S)NMe2 (3). 2 reacts with 2-benzoyl pyridine (PhCOPy-2) to form the lead(II) alkoxide LPbOC(NMe2)Ph(2-Py) (4) by nucleophilic addition of “NMe2” to the carbon oxygen double bond. The reaction of stable N-heterocyclic germylene L1Ge [L1 = CH{(C=CH2)(CMe)(2,6-iPr2C6H3N)2}] with hydrazine yields the germanium(II) substituted hydrazide LGeNHNH2 (5) by cleavage of one N−H bond of hydrazine. Finally, attempts to isolate lead(II) hydride LPbH from the reaction of 2 with phenylsilane (PhSiH3) failed, and instead LPbN(2,6-iPr2C6H3){C(CH3)CHC(CH3)N(2,6-iPr2C6H3)} (6) was obtained in very low yield. We are able to prove this only by single crystal X-ray structural analysis. Compounds 1, 2, 3, 4, and 5 were characterized by microanalysis, electron impact (EI) mass spectrometry, and multinuclear NMR spectroscopy. Furthermore compounds 1, 2, 5, and 6 were characterized by single crystal X-ray structural analysis, with the result that they are exhibiting monomeric structures in the solid state with trigonal-pyramidal environment at the metal center and a stereochemically active lone pair.