- 作者: 陳竹亭 ; 葉雨松 ; 曾文華 等
- 作者服務機構: 台灣大學化學系
- 中文摘要: Treatment of trans-Pt(COCOPh)(Cl)(PPh/sub 3/)/sub 2/ with AgBF/sub 4/ in THF led to the formation of a metastable complex trans-.lbrak.Pt(COCOPh)(THF)(PPh/sub 3/)/sub 2/.rbrak.(BF/sub 4/) which readily underwent ligand substitution to give a cationic aqua complex trans-.lbrak.Pt(COCOPh)(OH/sub 2/)(PPh/sub 3/)/sub 2/.rbrak.(BF/sub 4/)(5a). Complex 5a has been characterized spectroscopically and crystallographically. Analogous reaction of trans-Pt(COCOOMe)(Cl)(PPh/sub 3/)/sub 2/ with Ag(CF/sub 3/ SO/sub 3/) in dried CH/sub 2/Cl/sub 2/ was found first to yield a methoxyoxalyl triflato complex trans-Pt(COCOOMe)(OTf)(PPh/sub 3/)/sub 2/. Attempts to crystallize the triflato product in CH/sub 2/Cl/sub 2//n-hexane under ambient conditions also afforded an aqua complex of the triflate salt trans-.lbrak.Pt(COCOOMe)(OH/sub 2/)(PPh/sub 3/)/sub 2/.rbrak.(CF/sub 3/SO/sub 3/) (5b). Complex 5a in a noncoordinating solvent such as CH/sub 2/Cl/sub 2/ or CHCl/sub 3/ suffered spontaneous decarbonylation to form first cis-.lbrak.Pt(COPh)(CO)(PPh/sub 3/)/sub 2/.rbrak.(BF/sub 4/)(3a) then the thermodynamically stable isomer trans-.lbrak.Pt(COPh)(CO)(PPh/sub 3/)/sub 2/.rbrak.(BF/sub 4/)(3b). Crystallization of complex 3b under ambient conditions resulted in an aqua benzoyl complex trans-.lbrak.Pt(COPh)(OH/sub 2/)(PPh/sub 3/)/sub 2/.rbrak.(BF/sub 4/)(7). The replacement of the H/sub 2/O ligand in complex 7 by CO was done simply by bubbling CO into the solution of 7. The single crystal structures of 5b and 7 have been determined by X-ray diffraction. The distances of the Pt-O bonds in 5a, 5b, and 7 support that the aqua ligand is a weak donor in such cationic aquaorganoplatinum(II) complexes, in agreement with their lability to the substitution reactions.
- 英文摘要: --
- 中文關鍵字: .Alpha.-Ketoacyl Complex; Aquaorgano Complex; Weak Donor Ligand; Platinum; Complex; X-Ray Diffraction
- 英文關鍵字: 酮醯錯合物;錯合物;弱予體基;鉑(白金);X光繞射