Zinc hydrazides and alkoxyhydrazides: Organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures

Jana S, Fröhlich R, Mitzel NW (2006)
CHEMISTRY-A EUROPEAN JOURNAL 12(2): 592-599.

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Tetrameric [{RZn(NHNMe2)}(4)] (R - Me, Et), the first organometallic zinc hydrazides to be described, have been prepared by alkane elimination from dialkylzinc solutions and N,N-dimethylhydrazine. They were characterised by H-1 and C-13 NMR and IR spectroscopy, mass spectrometry, elemental analysis and X-ray crystallography. The compounds form asymmetric aggregates containing the novel Zn4N8 core; tetrahedra of Zn atoms bear the alkyl groups at Zn, with the triangular faces bridged by NHNMe2 substituents. The NH groups are connected to two Zn atoms, and the NMe2 groups to one. Hydrolysis of the compounds with water gives [(RZn)(4)(OH)(NHNMe2)(3)] as products, which also were characterised as described above. Higher yields of these hydroxo clusters were achieved in one-pot syntheses by reaction of dialkylzinc solutions with mixtures of N,N-dimethylhydrazine and water. They contain Zn4N6O cages, in which one hydroxide in the tetrameric hydrazides described above replaces one NHNMe2 group. Similar products can be prepared with alkoxy instead of hydroxy groups, in analogous one-pot syntheses with alcohols. Alcoholysis of [EtZn(NHNMe2)](4) with methanol or ethanol gave zinc trishydrazide monoalkoxides, [(EtZn)(4)(OR)(NHNMe2)(3)] (R = Me, Et), which have constitutions analogous to the monohydroxides. ne organozinc bishydrazide bisalkoxides [(MeZn)(4)(NHNMe2)(2)(OEt)(2)] and [(EtZn)(4)(NHNMe2)(2)(OEt)(2)] were obtained in one-pot reactions from dialkylzinc solutions with mixtures of the hydrazine and alcohol, and their crystal structures, confirmed by spectroscopic methods in solution, show an unsymmetrical aggregation with the novel Zn4N4O2 cage structure.
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Jana S, Fröhlich R, Mitzel NW. Zinc hydrazides and alkoxyhydrazides: Organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures. CHEMISTRY-A EUROPEAN JOURNAL. 2006;12(2):592-599.
Jana, S., Fröhlich, R., & Mitzel, N. W. (2006). Zinc hydrazides and alkoxyhydrazides: Organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures. CHEMISTRY-A EUROPEAN JOURNAL, 12(2), 592-599.
Jana, S., Fröhlich, R., and Mitzel, N. W. (2006). Zinc hydrazides and alkoxyhydrazides: Organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures. CHEMISTRY-A EUROPEAN JOURNAL 12, 592-599.
Jana, S., Fröhlich, R., & Mitzel, N.W., 2006. Zinc hydrazides and alkoxyhydrazides: Organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures. CHEMISTRY-A EUROPEAN JOURNAL, 12(2), p 592-599.
S. Jana, R. Fröhlich, and N.W. Mitzel, “Zinc hydrazides and alkoxyhydrazides: Organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 12, 2006, pp. 592-599.
Jana, S., Fröhlich, R., Mitzel, N.W.: Zinc hydrazides and alkoxyhydrazides: Organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures. CHEMISTRY-A EUROPEAN JOURNAL. 12, 592-599 (2006).
Jana, S., Fröhlich, R., and Mitzel, Norbert W. “Zinc hydrazides and alkoxyhydrazides: Organometallic compounds with novel Zn4N8, Zn4N6O and Zn4N4O2 cage structures”. CHEMISTRY-A EUROPEAN JOURNAL 12.2 (2006): 592-599.
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Redshaw C, Jana S, Shang C, Elsegood MR, Lu X, Guo ZX., Chem. Commun. (Camb.) 46(47), 2010
PMID: 21049112
Unique formation of mono-, tetra- and nona-nuclear zinc complexes from protonolysis reactions of [Zn(dmpzm)Et2].
Cheng ML, Li HX, Liu LL, Wang HH, Zhang Y, Lang JP., Dalton Trans (11), 2009
PMID: 19259572

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