large cone angles give only the anti isomer. Disubstituted complexes [Re2(μ-H)(μ-Snaph)(CO)6L2] [L = NCMe (3a), pyridine (3b), PPh3 (3c)] and [Re2(μ-H)(μ-Snaph)(CO)6(μ-L–L)] [L–L = dppm (4a), dppe (4b)] were prepared in a similar way. The reaction of [Re2(μ-H)(μ-SH)(CO)8] 5 with one equivalent of tmno and PPh3 gave [Re2(μ-H)(μ-SH)(CO)6(PPh3)2] 6 in 38% yield. Compound 6 is rigid on the timescale of 31P
氢化
硫桥联的dirhenium配合物[Re 2(μ-H)(μ-Snaph)(CO)8 ] 1(naph =2-
萘基)已被调查。前一种复合物很容易用一当量的tmno(
三甲胺-N-氧化物),然后添加一个
配体L给出具有通式[Re 2(μ-H)(μ-Snaph)(CO)7 L]的配合物[L = NCMe(2a),NC(Bu t)(2b),
吡啶(2c),PH 3(2d),PMe 3(2e),H 2 P(p -C 6 H 4 OMe)(2f),PPh 3(2g),P(OMe)3(2h)]。L始终相对于Re–(μ-SR)–Re平面垂直于Re原子之一。的情况下
配体具有小的锥角,发现了两个异构体。它们在L相对于连接在C上的取代基R的相对取向上有所不同
硫基桥(顺式和反式异构体)。取决于温度的2D-EXSY核磁共振用2a溶解在CDCl 3中的实验证明,这两种异构体都处于动态平衡,这是基于桥连
硫的
金字塔反演。确定该过程在298