Synthesis and structural characterization of (perfluoroalkyl)fluoroiridium(III) and (perfluoroalkyl)methyliridium(III) compounds

被引:23
作者
Bourgeois, Cheryl J.
Garratt, Shaun A.
Hughes, Russell P. [1 ]
Larichev, Roman B.
Smith, Jeremy M.
Ward, Antony J.
Willemsen, Stefan
Zhang, Donghui
DiPasquale, Antonio G.
Zakharov, Lev N.
Rheingold, Arnold L.
机构
[1] Dartmouth Coll, Dept Chem, Burke Labs 6128, Hanover, NH 03755 USA
[2] Univ Calif San Diego, Dept Chem, La Jolla, CA 92093 USA
关键词
D O I
10.1021/om060267s
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A new family of metal perfluoroalkyl fluoro compounds has been obtained by treatment of the iodo precursors Cp* Ir(PMe3)(R-F) I with AgF in CH2Cl2 solution in the dark to give Cp* Ir(PMe3)(R-F) F (R-F = CF3, CF2CF3, CF2CF2CF3, CF(CF3)(2), CF(CF3)(CF2CF3)). The molecular structures of the compounds with RF) CF2CF3, CF2CF2CF3, CF(CF3)(2) have been determined crystallographically. These fluoro compounds provide a ready and reproducible route to the analogous methyl complexes Cp* Ir( PMe3)( R-F) CH3, by treatment with exactly 0.5 equiv of Zn(CH3)(2) at low temperatures in toluene. Alkylation with other reagents such as CH3Li and Cp2Zr(CH3)(2) leads to inseparable mixtures. This metathesis of Ir-F and Zn-CH3 represents the only way to date for the clean reproducible synthesis of Cp* Ir(PMe3)( R-F) CH3 compounds containing primary perfluoroalkyl groups. The molecular structures of Cp* Ir(PMe3)( R-F) CH3 (R-F = CF2CF3, CF2CF2CF3) have been determined crystallographically.
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收藏
页码:3474 / 3480
页数:7
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