The Deprotonated Iminophosphorane o-C6H4PPh2P=NSiMe3 as a Novel Chelating Ligand in Organocopper(I) and -zinc(II) Chemistry
✍ Scribed by Stefan Wingerter; Heinz Gornitzka; Guy Bertrand; Dietmar Stalke
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 186 KB
- Volume
- 1999
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Lithiation of triphenyl(trimethylsilylimino)phosphorane zinc complex [Zn(o-C 6 H 4 PPh 2 NSiMe 3 ) 2 ] (3). Reaction with CuCl 2 gives access to the new diiminophosphorane (o-Ph 3 P=NSiMe 3 with MeLi gives the ortho-metallated species [Li(o-C 6 H 4 PPh 2 NSiMe 3 )] 2 •Et 2 O (1), which exhibits all the C 6 H 4 PPh 2 NSiMe 3 ) 2 (4) through oxidative coupling at the ortho positions. In all the metal complexes, the Ph 2 P=NSiMe 3 requirements of an organometallic ligand capable of sidearm donation. The deprotonated ortho-phenyl carbon atom residue acts as a side-arm donating group through the nitrogen atom. The intermolecular NǞCu donor bond in 2 is gives access to metal-carbon σ bonds in transmetallation reactions, while the Ph 2 P=NSiMe 3 moiety can donate to the as short as copper-amide bonds, while the NǞZn bond lengths in 3 are in the region normally found for donor bonds. same metal center through the imine nitrogen atom. In transmetallation reactions with CuBr, the dimeric Compound 4 is a molecule, possessing two Ph 2 P=NSiMe 3 moieties bridged by a biphenylene group. organocopper complex [Cu(o-C 6 H 4 PPh 2 NSiMe 3 )] 2 (2) is obtained, while application of ZnCl 2 yields the monomeric