Preparation and Characterization of Cobalt(III) Complexes Containing (CH<sub>3</sub>)<sub>2</sub>As(CH<sub>2</sub>)<i><sub>n</sub></i>As(CH<sub>3</sub>)<sub>2</sub>(<i>n</i>=2, 3)
作者:Katsumi Iwata、Masaaki Kojima、Junnosuke Fujita
DOI:10.1246/bcsj.58.3003
日期:1985.10
Twelve new complexes, trans-[CoX2(dmae or dmap)2]+ (X=Cl, Br, I; dmae=1,2-bis(dimethylarsino)ethane, dmap=1,3-bis(dimethylarsino)propane), cis-[CoX2(dmap)2] (X=Cl, Br), [Co(CO3)(dmae or dmap)2]+, and [Co(acac)3−n(dmap)n]n+(n=0, 1, 2; acac=2,4-pentanedionate ion) were prepared and characterized. From a comparison of the 1A1g→1Eg (D4h) d-d absorption bands of analogous trans-dichloro complexes of phosphines
十二个新配合物,反式-[CoX2(dmae or dmap)2]+ (X=Cl, Br, I; dmae=1,2-双(二甲基砷)乙烷, dmap=1,3-双(二甲基砷)丙烷),顺式-[CoX2(dmap)2] (X=Cl, Br)、[Co(CO3)(dmae 或 dmap)2]+ 和 [Co(acac)3−n(dmap)n]n+(n=0 , 1, 2; acac = 2,4-戊二酸根离子) 被制备和表征。从类似的膦和胺的反式二氯配合物的 1A1g→1Eg (D4h) dd 吸收带的比较,表明 5B 族元素的光谱化学序列顺序为 P>As>N。对于碳酸配合物,观察到晶体场能级之间的电子间排斥大大减少。在 20.1–49.9 °C 的温度范围内,在甲醇中研究了顺式-[CoCl2(dmap)2]+ 异构化为反式异构体的过程。该速率对复合物浓度具有一阶依赖性。54.9 °C 时的速率常数,