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Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn 4 N 8 , Zn 4 N 6 O and Zn 4 N 4 O 2 Cage Structures
Author(s) -
Jana Surajit,
Fröhlich Roland,
Mitzel Norbert W.
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500626
Subject(s) - chemistry , zinc , zinc hydroxide , dimethylhydrazine , methanol , alkoxy group , alcohol , group 2 organometallic chemistry , hydrazine (antidepressant) , alkyl , medicinal chemistry , hydrolysis , organic chemistry , crystallography , inorganic chemistry , molecule , medicine , colorectal cancer , chromatography , cancer
Abstract Tetrameric [{RZn(NHNMe 2 )} 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 1 H and 13 C NMR and IR spectroscopy, mass spectrometry, elemental analysis and X‐ray crystallography. The compounds form asymmetric aggregates containing the novel Zn 4 N 8 core; tetrahedra of Zn atoms bear the alkyl groups at Zn, with the triangular faces bridged by NHNMe 2 substituents. The NH groups are connected to two Zn atoms, and the NMe 2 groups to one. Hydrolysis of the compounds with water gives [(RZn) 4 (OH)(NHNMe 2 ) 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 Zn 4 N 6 O cages, in which one hydroxide in the tetrameric hydrazides described above replaces one NHNMe 2 group. Similar products can be prepared with alkoxy instead of hydroxy groups, in analogous one‐pot syntheses with alcohols. Alcoholysis of [EtZn(NHNMe 2 )] 4 with methanol or ethanol gave zinc trishydrazide monoalkoxides, [(EtZn) 4 (OR)(NHNMe 2 ) 3 ] (R = Me, Et), which have constitutions analogous to the monohydroxides. The organozinc bishydrazide bisalkoxides [(MeZn) 4 (NHNMe 2 ) 2 (OEt) 2 ] and [(EtZn) 4 (NHNMe 2 ) 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 Zn 4 N 4 O 2 cage structure.