[Rh_2(O_2CMe)_4]与若干含氮配体的加合物

Some New Nitrogen-coordinated Adducts of [Bh_2(O_2CMe)_4]

合成了10个[Rh_2(O_2CMe)_4]与含氮配体的加合物:[Rh_2(O_2CMe)_4L_2),L=哌啶,4-氨基安替比林,3-氨基苯二甲酰环肼(鲁米诺),2,5-二苯基噁唑(PPO),1,4-二(2-(5-苯基噁唑基)]苯(POPOP);[Rh_2(O_2CMe)_4L_2]·H_2O,L=苯骈噻唑,1-萘胺;[Rh_2(O_2CMe)_4L]_n,L=外消旋—5,7,7,12,12,14-六甲基—1,4,8,11-四氮杂环十四烷(tet b),4,4′-二胺基-3,3′-二甲基联苯(邻联甲苯胺)。研究了它们的红外光谱,测定了它们在乙醇—苯中的稳定常数,观察到logβ_2与加合物电子光谱谱带I的波数v_1呈正相关关系。讨论了π相互作用对轴向Rh-L成键的贡献。

Ten N-coordinated adducts of [Rh2(O2CMe)4] were synthesized. [Rh2(O2CMe)4L2] , L = piperidiae, 4-aminoantipyrine, luminol, 2,5-diphenyloxazole, and 1,4-bis (5-phenyl-2-oxazolyl) benzene; [Rh2(O2CMe)4L2]·H2O, L = benzothiazole and 1-naphthyl-amine; [Rh2(O2CMe)4L]2, L = rac-5, 7, 7, 12, 12, 14-hexamethyl-l, 4, 8, 11-tetra-azacyclotetradecane and o-tolidine. Their infrared spectra were recorded and discussed. The stability constants of these adducts in ethanol-benzene mixture were determined by spectrophotometry. A positive correlation between log β2 and γ1, the wavenumber of band I in their electronic spectra, has been observed. The contribution of π interaction to the bonding between Rh and the axially coordinated ligand is discussed.