Organometallic Fluorides of Zirconium and Hafnium in the Synthesis of Carboxylate Complexes: Molecular Structures of [{(5-C
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- 作者：Hendrik Dorn ; Syed A. A. Shah ; Emilio Parisini ; Mathias Noltemeyer ; Hans-Georg Schmidt ; and Herbert W. Roesky
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：November 20, 1996
- 年：1996
- 卷：35
- 期：24
- 页码：7181 - 7184
- 全文大小：303K
- 年卷期：v.35,no.24(November 20, 1996)
- ISSN：1520-510X
文摘
The reaction of[(
5-C5Me5)ZrF3]and[(5-C5Me5)HfF3]with Me3SiOCOCF3 yields the dinuclearcomplexes[{(5-C5Me5)ZrF(OCOCF3)2}2](1) and[{(5-C5Me5)HfF(OCOCF3)2}2](2), regardless of the molar ratio employed.[(5-C5Me5)2ZrF2]reacts with 1 and 2 equiv of Me3SiOCOCF3to form the mononuclear compounds[(5-C5Me5)2Zr(OCOCF3)2] (3) and[(5-C5Me5)2ZrF(OCOCF3)](4), respectively. The molecular structures of1 and 3 havebeen determined by single-crystal X-ray analysis: 1,triclinic, P
, a = 9.508(3) Å,b = 11.002(4) Å, c =17.528(3)Å, 
= 78.55(4), 
= 76.80(2), 
=87.51(2)
, V = 1750(1) Å3,Z = 2, R = 0.0378; 3, monoclinic,C2/c, a =18.553(4) Å, b = 9.110(2) Å, c =16.323(3) Å, = 114.88(3), V =2503(1) Å3, Z = 4, R =0.0457. Compound1 shows bridging bidentate and chelating carboxylate ligandsas well as bridging fluorine atoms. The zirconiumatoms are seven coordinated and have an 18-electron configuration.X-ray studies of 3 reveal two structuralcomponents where the carboxylate ligands coordinate in a monodentate(major component) and a chelating manner(minor component).
5-C5Me5)ZrF3]and[(5-C5Me5)HfF3]with Me3SiOCOCF3 yields the dinuclearcomplexes[{(5-C5Me5)ZrF(OCOCF3)2}2](1) and[{(5-C5Me5)HfF(OCOCF3)2}2](2), regardless of the molar ratio employed.[(5-C5Me5)2ZrF2]reacts with 1 and 2 equiv of Me3SiOCOCF3to form the mononuclear compounds[(5-C5Me5)2Zr(OCOCF3)2] (3) and[(5-C5Me5)2ZrF(OCOCF3)](4), respectively. The molecular structures of1 and 3 havebeen determined by single-crystal X-ray analysis: 1,triclinic, P, a = 9.508(3) Å,b = 11.002(4) Å, c =17.528(3)Å, = 78.55(4), = 76.80(2), =87.51(2), V = 1750(1) Å3,Z = 2, R = 0.0378; 3, monoclinic,C2/c, a =18.553(4) Å, b = 9.110(2) Å, c =16.323(3) Å, = 114.88(3), V =2503(1) Å3, Z = 4, R =0.0457. Compound1 shows bridging bidentate and chelating carboxylate ligandsas well as bridging fluorine atoms. The zirconiumatoms are seven coordinated and have an 18-electron configuration.X-ray studies of 3 reveal two structuralcomponents where the carboxylate ligands coordinate in a monodentate(major component) and a chelating manner(minor component).