金属结合口袋侧翼具有庞大芳基的菲咯啉基配体能够合成和详细研究铜( I )、银( I )和金( I )的乙烯配合物,包括[{2,9-bis]的结构数据(2,4,6-三异丙基苯基)-1,10-菲咯啉}M(C 2 H 4 )][SbF 6 ] (M = Cu, Ag, Au),此外,还有一种相关的铜( I )-乙烯配合物还报道了高度氟化的配体。金 ( I ) 对乙烯部分有显着影响,从 NMR 中乙烯碳信号的显着高场配位偏移和乙烯 C 的延长可以明显看出 C键长。在这一系列等阻的第 11 族金属-乙烯络合物中,银 ( I ) 与乙烯形成最弱的键。初步催化研究强调了铜配合物的潜力,特别是那些具有弱配位支持配体的铜配合物,作为通过三氟甲基卡宾插入进行C(sp 3 )–H官能化的有效催化剂。
Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a. The upper limit of Delta G double dagger, assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with Delta G(298)double dagger = 12.9 +/- 0.1 kcal/mol, while the exchange is the slowest in Au complex 9, with Delta G(298)double dagger = 16.7 +/- 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.
Synthesis and Characterization of the Gold(I) Tris(ethylene) Complex [Au(C2H4)3][SbF6]
作者:H. V. Rasika Dias、Mauro Fianchini、Thomas R. Cundari、Charles F. Campana