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

Abstract

The beta-diketiminate substituted germanium(II) and lead(II) dimethylamides, LGeNMe(2) (1) and LPbNMe(2) (2), [L = CH{(CMe)(2)(2,6-iPr(2)C(6)H(3)N)(2)}] have been synthesized by the reaction of LiNMe(2) 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)NMe(2) (3). 2 reacts with 2-benzoyl pyridine (PhCOPy-2) to form the lead(II) alkoxide LPbOC(NMe(2))Ph(2-Py) (4) by nucleophilic addition of "NMe(2)" to the carbon oxygen double bond. The reaction of stable N-heterocyclic germylene L(1)Ge [L(1) = CH{(C=CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}] with hydrazine yields the germanium(II) substituted hydrazide LGeNHNH(2) (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 (PhSiH(3)) failed, and instead LPbN(2,6-iPr(2)C(6)H(3)){C(CH(3))CHC(CH(3))=N(2,6-iPr(2)C(6)H(3))} (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.