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The Deprotonated Iminophosphorane o ‐C 6 H 4 PPh 2 P=NSiMe 3 as a Novel Chelating Ligand in Organocopper(I) and ‐zinc(II) Chemistry
Author(s) -
Wingerter Stefan,
Gornitzka Heinz,
Bertrand Guy,
Stalke Dietmar
Publication year - 1999
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/(sici)1099-0682(199901)1999:1<173::aid-ejic173>3.0.co;2-t
Subject(s) - chemistry , transmetalation , deprotonation , oxidative addition , medicinal chemistry , ligand (biochemistry) , amide , imine , zinc , organometallic chemistry , stereochemistry , polymer chemistry , organic chemistry , crystal structure , catalysis , ion , biochemistry , receptor
Lithiation of triphenyl(trimethylsilylimino)phosphorane 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 requirements of an organometallic ligand capable of side‐arm donation. The deprotonated ortho ‐phenyl carbon atom gives access to metal–carbon σ bonds in transmetallation reactions, while the Ph 2 P=NSiMe 3 moiety can donate to the same metal center through the imine nitrogen atom. In transmetallation reactions with CuBr, the dimeric organocopper complex [Cu( o ‐C 6 H 4 PPh 2 NSiMe 3 )] 2 ( 2 ) is obtained, while application of ZnCl 2 yields the monomeric 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 ‐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 residue acts as a side‐arm donating group through the nitrogen atom. The intermolecular N→Cu donor bond in 2 is as short as copper–amide bonds, while the N→Zn bond lengths in 3 are in the region normally found for donor bonds. Compound 4 is a molecule, possessing two Ph 2 P=NSiMe 3 moieties bridged by a biphenylene group.