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Synthesis and Isomerisation Reactions of Tetranuclear and Octanuclear (Carbamato)zinc Complexes
Author(s) -
Haywood Peter F.,
Hill Matthew R.,
Roberts Nicholas K.,
Craig Donald C.,
Russell Jennifer J.,
Lamb Robert N.
Publication year - 2008
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700736
Subject(s) - chemistry , zinc , isomerization , dimer , stoichiometry , nuclear magnetic resonance spectroscopy , transition metal , alkane , solvent , hydrolysis , medicinal chemistry , crystallography , stereochemistry , organic chemistry , catalysis
A new series of (diisopropylcarbamato)(oxido)zinc complexes were obtained by innovative synthetic approaches. The (carbamato)zinc clusters [Zn 4 (μ 4 ‐O)(O 2 CN i Pr 2 ) 6 ] ( 1 ) and [Zn 8 (μ 4 ‐O) 2 (O 2 CN i Pr 2 ) 12 ] ( 2 ) were synthesised by an identical reaction procedure involving protolysis of ZnEt 2 with i Pr 2 NH/CO 2 and followed by stoichiometric hydrolysis. Recrystallisation of the reaction product from nitrile solvents yielded the tetrazinc complex 1 . Conversely, recrystallisation from alkane solvents yielded crystals of the octazinc complex 2 . The two structural isomers were readily interconverted simply by recrystallisation from the appropriate solvent. Both complexes were structurally characterised by X‐ray crystallography. The tetrazinc complex 1 has the quintessential basic zinc acetate type structure. Its dimer, the octazinc complex 2 is a new derivative of the [M 8 (μ 4 ‐O) 2 (O 2 CN i Pr 2 ) 12 ] class, examples of which are known for all other first‐row transition metals. The solution chemistry was investigated using variable‐temperature NMR spectroscopy and ESI‐MS. The new synthetic approach offers a route to other similar complexes. Thus, using Et 2 NH in place of i Pr 2 NH yielded the known complex [Zn 4 (μ 4 ‐O)(O 2 CNEt 2 ) 6 ] ( 3 ).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)