The new [Co5C(CO)12}AuCo(CO)4}]â, [1]â, cluster has been obtained from the reaction of [Co6C(CO)15]2â with two equivalents of [AuCl4]â. [1]â reacts with an excess of HBF4 resulting in the formation of [Co5C(CO)12}2Au]â, [2]â. The new derivatives [Co5C(CO)12(AuPPh3)], 3, and [Co5C(CO)11(AuPPh3)3], 4, have been obtained by reacting [2]â with two and four equivalents of [Au(PPh3)Cl], respectively. All the new species have been structurally characterised by means of X-ray crystallography as their [NEt4][1], [NEt4][2], [NMe3(CH2Ph)][2], 3 and 4·thf·0.5C6H14 salts and solvates. [2]â may be viewed as a homoleptic Au(I) complex containing two [Co5C(CO)12]â clusters as ligands. Similarly, [1]â and 3 are heteroleptic Au(I) complexes containing one [Co5C(CO)12]â cluster ligand as well as [Co(CO)4]â or PPh3. Conversely, 4 contains the [Co5C(CO)11]3â cluster stabilized by three [AuPPh3]+ fragments. [1]â and [2]â have been investigated in solution by means of electrochemical and spectroelectrochemical methods, revealing a very rich redox propensity to form the closely related [1]nâ (n = 1â3) and [2]nâ (n = 0â3) species.
新的[Co5C(CO)12}AuCo(CO)4}]â,[1]â,是由[Co6C(CO)15]2â与两个当量的[AuCl4]â反应得到的。[1]â与过量的
HBF4 反应生成[Co5C(CO)12}2Au]â,[2]â。[2]â分别与两个和四个当量的[Au(PPh3)Cl]反应,得到了新的衍
生物[Co5C(CO)12(AuPPh3)]3和[Co5C(CO)11(AuPPh3)3]4。通过 X 射线晶体学方法,对所有新品种的[NEt4][1]、[NEt4][2]、[NMe3(CH2Ph)][2]、3 和 4Â-thfÂ-0.5C6H14盐和溶质进行了结构表征。[2]â可以看作是含有两个[Co5C(CO)12]â团簇作为
配体的同性
金(I)配合物。同样,[1]â 和 3 是异性 Au(I)配合物,含有一个[Co5C(CO)12]â 簇
配体以及[Co(CO)4]â 或 PPh3。相反,4 复合物含有[Co5C(CO)11]3â簇,由三个[AuPPh3]+片段稳定。通过电
化学和光谱电
化学方法对溶液中的[1]â和[2]â进行了研究,发现它们具有非常丰富的氧化还原倾向,能形成密切相关的[1]nâ(n = 1â3)和[2]nâ(n = 0â3)物种。