Sterically Hindered and Robust Pnictogen Ligands Derived from Carboranes: Synthesis and X-ray Structure Determination of Tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine, Tri
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- 作者：Arienne S. King ; George Ferguson ; James F. Britten ; and John F. Valliant
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：May 31, 2004
- 年：2004
- 卷：43
- 期：11
- 页码：3507 - 3513
- 全文大小：168K
- 年卷期：v.43,no.11(May 31, 2004)
- ISSN：1520-510X
文摘
Sterically hindered phosphine and arsine ligands derived from ortho-carborane were synthesized and characterizedby X-ray crystallography. Tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine, 2 (crystal data, hexagonal,space group P63, a = b = 12.251(3) Å, c = 11.514(4) Å, 
= 
= 90
, 
= 120, V = 1496.6(7) Å3, Z = 2,R1 = 0.0568) and tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))arsine, 3 (crystal data, hexagonal, space groupP63, a = b = 12.330(3) Å, c = 11.474(4) Å, = = 90, = 120, V = 1510.7(7) Å3, Z = 2, R1 = 0.0930)were prepared in 82% and 68% yield, respectively. The phosphine ligand is resistant to air-oxidation but wasconverted to corresponding oxide when heated with hydrogen peroxide. The tertiary carboranyl phosphine reactedwith (Tht)AuCl to yield chloro(tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine)gold(I), 4 (crystal data,monoclinic, space group P21/c, a = 19.101(4) Å, b = 12.167(2) Å, c = 13.846(3) Å, = = 90, = 91.13(3), V = 3217.2(11) Å3, Z = 4, R1 = 0.0396) in 82% yield. From the X-ray structure of the gold complex, thecone angle of the phosphine was determined to be 213(2), which is among the largest values reported to date.
= = 90, = 120, V = 1496.6(7) Å3, Z = 2,R1 = 0.0568) and tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))arsine, 3 (crystal data, hexagonal, space groupP63, a = b = 12.330(3) Å, c = 11.474(4) Å, = = 90, = 120, V = 1510.7(7) Å3, Z = 2, R1 = 0.0930)were prepared in 82% and 68% yield, respectively. The phosphine ligand is resistant to air-oxidation but wasconverted to corresponding oxide when heated with hydrogen peroxide. The tertiary carboranyl phosphine reactedwith (Tht)AuCl to yield chloro(tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine)gold(I), 4 (crystal data,monoclinic, space group P21/c, a = 19.101(4) Å, b = 12.167(2) Å, c = 13.846(3) Å, = = 90, = 91.13(3), V = 3217.2(11) Å3, Z = 4, R1 = 0.0396) in 82% yield. From the X-ray structure of the gold complex, thecone angle of the phosphine was determined to be 213(2), which is among the largest values reported to date.