Oxidative addition of 1,2,5,6-Tetrathiocins to Co(I): A Re-Examination of Crown Ether Functionalized Benzene Dithiolate Cobalt(III) Complexes
作者:Lara K. Watanabe、Zeinab S. Ahmed、John J. Hayward、Elodie Heyer、Charles L. B. Macdonald、Jeremy M. Rawson
DOI:10.1021/acs.organomet.1c00559
日期:2022.2.14
5″-crown-functionalized dibenzo-1,2,5,6-tetrathiocins, [(OCH2CH2)nOC6H2S2]2 (1, n = 4; 2, n = 5), to the Co(I) complex CpCo(CO)2 under microwave irradiation in toluene affords 16e– Co(III) dithiolate complexes CpCoS2C6H2O(CH2CH2O)n} 3 (n = 4) and 4 (n = 5) in 71–75% recovered yield. Complexes 3 and 4 were characterized by X-ray diffraction. Compound 3 was found to be polymorphic, crystallizing as the
4',4”,5',5”-冠官能化二苯并-1,2,5,6-四硫辛的氧化加成,[(OCH 2 CH 2 ) n OC 6 H 2 S 2 ] 2 ( 1 , n = 4; 2 , n = 5), 在甲苯中微波辐照 Co(I) 配合物 CpCo(CO) 2得到 16 e - Co(III) 二硫醇盐配合物 CpCoS 2 C 6 H 2 O(CH 2 CH 2 O) n } 3 ( n = 4) 和4 ( n = 5),回收率为 71-75%。配合物3和4通过 X 射线衍射进行了表征。发现化合物3是多晶型的,结晶为 16 e –单体3或 18 e –二聚体 ( 3 ) 2,具体取决于反应条件。与之前的文献建议在3和 s-block 阳离子之间形成 1:1 配合物相比, 3与s-block 金属盐 M[BPh 4 ](M = Na、K、Rb 和 Cs)的反应形成了2:1 配合物 [CpCo(S