Compound 1 is intensely colored due to low-energy, metal-based electronic transitions between the HOMO and HOMO-2 and the LUMO. Compound 1 reacts with I2 to yield Re2(CO)8(μ-AuPPh3)(μ-I), 3, and the known compound Re2(CO)8(μ-I)2, 4, by substitution of the bridging AuPPh3 groups with bridging iodide ligands. Compound 3 is electronically saturated, 34 valence electrons, and contains a formal Re–Re single
化合物重新2(CO)8(μ-AuPPh 3)2,1,二聚体的Re(CO)4(μ-AuPPh 3)和斧,斧-Re的2(CO)8(PPH 3)2分别为从紫外可见辐射诱导的化合物Re(CO)5 [Au(PPh 3)]的脱羰反应中获得。化合物1包含两个由两个AuPPh 3基团桥接的rh原子。该络合物具有32个价电子,并且在形式上不饱和两个电子。Re-Re键距(以1为单位)通过单晶结构分析发现,它非常短(Re-Re = 2.9070(3)Å)。通过DFT计算分析研究了1中
金属-
金属键的性质,这不仅为σ键提供了证据,而且还为两个rh原子之间直接存在显着的互补π键提供了证据。RE的电子结构2(CO)8(μ-H)2,2,类似地分析,并且与比较1。化合物1由于HOMO和HOMO-2与LUMO之间的低能
金属基电子跃迁而强烈着色。化合物1与I 2反应生成Re 2(CO)8(μ-AuPPh 3)(μ-I),3,以