Studies on nucleophilic additions at bridging vinyl ligands in triosmium clusters
作者:Antony J. Deeming、Peter J. Manning
DOI:10.1016/0022-328x(84)80055-8
日期:1984.4
The bridging vinyl clusters [HOs3(CHCHR)(CO)10] (R = H, Ph, or n-Bu) react with PMe2Ph to give the zwitterionic adducts [HOs3(CHCHRPMe2Ph)(CO)10] which contain μ2-alkylidene ligands. The adducts are not formed so readily when R = Ph or n-Bu but most readily when polar solvents are used. All three CHCHR complexes add cyanide ion irreversibly to give the anionic clusters which were isolated as [N(
桥接的乙烯基簇[HOs 3(CH = CHR)(CO)10 ](R = H,Ph或n-Bu)与PMe 2 Ph反应生成两性离子加合物[HOs 3(CHCHRPMe 2 Ph)(CO)10 ]含有μ 2 -烷叉基配位体。当R = Ph或n-Bu时,加合物不易形成,但在使用极性溶剂时最容易形成。所有三种CHCHR络合物均不可逆地添加氰化物离子,得到的阴离子簇被分离为[N(PPh 3)2 ] [HOs 3(CHCHRCN)(CO)10]。有红外证据表明可以添加其他各种阴离子。酸会逆转甲醇盐的添加,但HCl与氰化物加合物[HOs 3(CHCH 2 CN)(CO)10 ] -反应生成[HOs 3 Cl(CO)10 ]和EtCN。没有获得在[HOs 3(PhCCHPh)(CO)10 ]处亲核加成的证据。