General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides.
Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.
Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
Wai-Lun
WL
Man
Hoi-Ki
HK
Kwong
William W Y
WW
Lam
Jing
J
Xiang
Tsz-Wing
TW
Wong
Wing-Hong
WH
Lam
Wing-Tak
WT
Wong
Shie-Ming
SM
Peng
Tai-Chu
TC
Lau
D000975:Antioxidants; D002614:Chelating Agents; D018360:Crystallography, X-Ray; D005029:Ethylenediamines / Q000737:chemistry*; D015394:Molecular Structure; D009584:Nitrogen; D017672:Nitrogen Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*
D000975:Antioxidants; D002614:Chelating Agents; D005029:Ethylenediamines; D017672:Nitrogen Compounds; D012428:Ruthenium; C011452:disalicylaldehyde ethylenediamine; D009584:Nitrogen