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- Title
Synthesis, Structure, and Reactivity of a Dimeric Zinc(I) Compound Stabilized by a Sterically Demanding Diiminophosphinate Ligand.
- Authors
Stasch, Andreas
- Abstract
The new sterically demanding aminoiminophosphorane Ph2P(NDip)(NHDip) (Dip=C6H3-2,6- iPr2; LH, 1) has been prepared as a precursor to the potassium complex [LK] ( 2) and a series of heteroleptic zinc(II) complexes, namely [(LZnBr)2] ( 3), [LZnMe] ( 4), [LZnEt] ( 5), and [(LZnI)2] ( 6). The products have been obtained either through a salt metathesis route by using complex 2 and ZnBr2 to give compound 3, through a direct reaction of ligand precursor 1 and ZnR2 (R=Me or Et) yielding complexes 4 or 5, respectively, or through iodination of complexes 4 or 5 by using I2 to afford compound 6. Reduction of the heteroleptic zinc(II) halide complexes 3 or 6 by using a dimeric magnesium(I) compound as a selective, stoichiometric, and soluble reducing agent afforded the new zinc(I) dimer [(LZn)2] ( 7) in good yield. Compounds 1- 7 were crystallographically and spectroscopically characterized and the coordination behavior of the diiminophosphinate ligand has been investigated and compared with related CN-based ligands. An initial reactivity study has been carried out on [(LZn)2] ( 7) by using small-scale reactions and the oxidative addition of small alkyl halides across the ZnZn bond has been found to generate equimolar amounts of the alkyl complexes 4 or 5 and the halide complexes 3 or 6, respectively.
- Publication
Chemistry - A European Journal, 2012, Vol 18, Issue 47, p15105
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201202560