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三配位釩金屬錯合物及其亞胺基衍生物
Thesis

三配位釩金屬錯合物及其亞胺基衍生物

蔡篤慰
Masters, 國立清華大學, 化學系
2004

Abstract

三配位 低配位 亞胺 釩氮三鍵 重氮烷 疊氮烷 vanadium three coordinate low coordinate imido VN triple bond diazoalkane organoazide
We have developed two new amino ligands [N,N’-cyclohexyl –(2,6-diisopropylphenyl) amino Lithium] and [N,N’-cyclohexyl –(2,4,6-trimethylphenyl) amino Lithium] reacting with VCl3(thf)3 to get two masked three coordinate complex: Complex 1 [VCl(THF)(N(Cy)dipp)2] and Complex 2 [VCl (THF)(N(Cy)dipp)2].To this bulkyl Complex 1,treat with N2C(H)TMS or N3R (R=Mes,TMS),we can get three organo imido vanadium complex product Complex 3 [(TMS-C(H)N2)VCl(THF)(N(Cy) dipp)2], Complex 4 [(Mes-N3)VCl(THF)(N(Cy)dipp)2],and Complex 5 [(TMS-N)VCl(THF)(N(Cy)dipp)2].We also treat a n-Butyl lithium deprotonating trimethylsilyldiazomethane with Complex 1 to get an unexpected product Complex 5 which lose a lithium cyanide and its side product Complex 6 [V(N(Cy)dipp)2 (CN)2Li(OEt)2]2 proving the formation of LiCN. So we can suppose the possible reaction way. In the other way, Complex 1 react with NaN3 affords a nitrido vanadium complex Complex 7 [V(N(Cy)dipp)2(μ-Cl)(μ-N) Na(OEt2)2]. We can get a similar result, Complex 8 [VCl(N(Cy) dipp)2(N-C(O)tBu)2] and Complex 9 [VCl(N(Cy)dipp)2(N-C(O)Ph)2] if we treat Complex 7 with pivaloyl chloride or benzoyl chloride.

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