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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 15, Number 5
BKCSDE 15(5)
May 20, 1994 

 
Title
Synthesis, Characterization, and Catalytic Properties of Gp 6 Metal Complexes of 1-N,N-dimethylaminomethyl-1',2-bis(diphenylphosphino)ferrocene (FcNPP). X-ray Crystal Structure of W(CO)4(η2-FcNPP(O)-P,N)
Author
Tae-Jeong Kim*, Yong-Hoon Kim, Eun-Jin Kim, Sang-Ho Oh, Hong-Seok Kim*, Jong-Hwa Jeong*
Keywords
Abstract
Reactions of 1',2-bis(diphenylphosphino)-l-(N,N-dimethylamino methyl)ferrocene (FcNPP) with M(CO)6 (M=Cr, Mo, W) in the presence of TMNO (Trimethylamine oxide) in a stoichiometric ratio of 1 : 1.5 : 3.5 produced a series of Gp 6 metal carbonyl derivatives with a variety of coordination modes: M(CO)4(η2-FcNPP-P,P) (M=Cr, Mo, W), M(CO)5(η1-FcNPP-P) (M=Mo, W), M2(CO)9(η1,η 2-FcNPP-P,P,N) (M=Cr, Mo), M2(CO)10(η1,η 1-FcNPP-P,P) (M=Cr, Mo, W), and W(CO)4(η 2-FcNPP(O)-P,N). All these complexes were characterized by microanalytical and spectroscopic techniques. In one case, the structure of W(CO)4(η2-FcNPP(O)-P,N) was determined by X-ray crystallography. Crystals are monocinic, space group P21/c, with a=10.147(2), b=19.902(3), c=19.821(4) Å, β=96.88(2)°, V=3974(l) Å3, Z=4, and Dcalc=l.64 g cm-3. The geometry around the central tungsten metal is a distorted octahedron, with the nitrogen and phosphorus atoms being cis to each other. Some of these complexes exhibited catalytic activities in the allylic oxidation and epoxidation of cholesterly acetate. Other oxidation products were also formed with the different chemical yields and product distribution depending upon the ligand and the central metal.
Page
379 - 386
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