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, tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))arsine and chloro(tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine)gold(I).
Sterically hindered phosphine and arsine ligands derived from ortho-carborane were synthesized and characterized by X-ray crystallography. Tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine, 2 (crystal data, hexagonal, space group P6(3), a = b = 12.251(3) A, c = 11.514(4) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 1496.6(7) A(3), Z = 2, R(1) = 0.0568) and tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))arsine, 3 (crystal data, hexagonal, space group P6(3), a = b = 12.330(3) A, c = 11.474(4) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 1510.7(7) A(3), Z = 2, R(1) = 0.0930) were prepared in 82% and 68% yield, respectively. The phosphine ligand is resistant to air-oxidation but was converted to corresponding oxide when heated with hydrogen peroxide. The tertiary carboranyl phosphine reacted with (Tht)AuCl to yield chloro(tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine)gold(I), 4 (crystal data, monoclinic, space group P2(1)/c, a = 19.101(4) A, b = 12.167(2) A, c = 13.846(3) A, alpha = gamma = 90 degrees, beta = 91.13(3) degrees, V = 3217.2(11) A(3), Z = 4, R(1) = 0.0396) in 82% yield. From the X-ray structure of the gold complex, the cone angle of the phosphine was determined to be 213(2) degrees, which is among the largest values reported to date.
King
Arienne S
AS
Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada L8S 4M1.
Ferguson
George
G
Britten
James F
JF
Valliant
John F
JF