Zinc hydrazides and hydrazide-alkoxides with cyclic and acyclic hydrazide substituents

The tetrameric organometallic zinc hydrazides the {(RZn)(4)[NHN(CH2)(n)](4)} (R = Me, Et, Pr-i and n = 5, 4) (1-6), were prepared by alkane elimination from dialkyl zinc solutions and the ring-substituted hydrazine derivatives I-aminopiperidine and 1-aminopyrrolidine at ambient temperature. They were characterized by NMR (H-1, C-13) and IR spectroscopy, by mass spec-xometry and by elemental analyses. The compounds form asymmetric aggregrates, containing Zn4N8 cores. Zinc trisalkoxide-monohydrazides can be prepared in one-pot syntheses by reacting dialkylzinc solutions simultaneously with alcohols and hydrazines. Reactions of dimethylzinc with isopropanol and monomethyl-hydrazine or mono-t-butylhydrazine in 2:1:1.03 ratio resulted in the formation of [(MeZn)(4)(NHNHR)((OPr)-Pr-i)(3)] [R = Me (7), Bu-t (8)]. In a similar fashion, dialkylzinc compounds react with 1-aminopiperidine and alcohol in 5:4:4 ratio to give {(RZn)(4)[NHN(CH2)(5)](OR')(3)]} [R = Me, R' = Pr-i (9); R = Et, R' = Et (10), Pr-i (11)]. These compounds were characterized as the above compounds. The structures of compounds 8 and 9 were also determined by crystal structure analyses. These compounds show an unsymmetrical aggregation with a Zn4N2O3 cage structure, confirmed by spectroscopic methods in solution.