Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Synthesis, Characterization, and Catalytic Properties of Gp 6 Metal Complexes of 1-N,N-dimethylaminomethyl-$1^{\prime}$,2-bis(diphenylphosphino)ferrocene (FcNPP). X-ray Crystal Structure of W$(CO)_4({\eta}^2-FcNPP(O)-P,N)$

  • Kim, Tae-Jeong (Department of Chemistry, Kyungpook National University) ;
  • Kim, Yong-Hoon (Department of Industrial Chemistry, Kyungpook National University) ;
  • Kim, Eun-Jin (Department of Industrial Chemistry, Kyungpook National University) ;
  • Oh, Sang-Ho (Department of Industrial Chemistry, Kyungpook National University) ;
  • Kim, Hong-Seok (Department of Industrial Chemistry, Kyungpook National University) ;
  • Jeong, Jong-Hwa (Department of Industrial Chemistry, Kyungpook National University)
  • Published : 1994.05.20
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Abstract

Reactions of 1',2-bis(diphenylphosphino)-l-(N,N-dimethylaminomethyl)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)$_4({\eta}^2$-FcNPP-P,P) (M=Cr, Mo, W), $M(CO)_5({\eta}^1-FcNPP-P) (M=Mo, W)\;,\; M_2(CO)_9({\eta}^1\;,\;{\eta}^2-FcNPP-P,P,N) (M=Cr, Mo)\;,\;M_2(CO)_{10}({\eta}^1\;,\;{\eta}^1-FcNPP-P,P) (M=Cr, Mo, W)\;, and\;W(CO)_4({\eta}^2-FcNPP(O)-P,N)$. All these complexes were characterized by microanalytical and spectroscopic techniques. In one case, the structure of W(CO)$_4({\eta}^2$-FcNPP(O)-P,N) was determined by X-ray crystallography. Crystals are monocinic, space group P$2_{1/C}$, with a=10.147(2), b=19.902(3), c=19.821(4) ${\AA},\;{\beta}=96.88(2)^{\circ},\;V=3974(l){\AA}^3$, Z=4, and $D_{calc}=1.64 g cm^{-3}$. 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.

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