Bortoluzzi Marco, Ciabatti Iacopo, Femoni Cristina, Funaioli Tiziana, Hayatifar Mohammad, Iapalucci Maria Carmela, Longoni Giuliano, Zacchini Stefano
Dipartimento di Scienze Molecolari e Nanosistemi, Ca' Foscari University of Venice, Dorsoduro, 2137-30123 Venezia, Italy.
Dalton Trans. 2014 Jul 7;43(25):9633-46. doi: 10.1039/c4dt00854e.
The new {Co5C(CO)12}Au{Co(CO)4}, , cluster has been obtained from the reaction of Co6C(CO)15 with two equivalents of AuCl4. reacts with an excess of HBF4 resulting in the formation of {Co5C(CO)12}2Au, . The new derivatives [Co5C(CO)12(AuPPh3)], , and [Co5C(CO)11(AuPPh3)3], , have been obtained by reacting 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][], [NEt4][], [NMe3(CH2Ph)][], and thf·0.5C6H14 salts and solvates. may be viewed as a homoleptic Au(i) complex containing two Co5C(CO)12 clusters as ligands. Similarly, and are heteroleptic Au(i) complexes containing one Co5C(CO)12 cluster ligand as well as Co(CO)4 or PPh3. Conversely, contains the Co5C(CO)11 cluster stabilized by three AuPPh3 fragments. and have been investigated in solution by means of electrochemical and spectroelectrochemical methods, revealing a very rich redox propensity to form the closely related (n = 1-3) and (n = 0-3) species.
新型[{Co₅C(CO)₁₂}Au{Co(CO)₄}]⁻簇合物是由[Co₆C(CO)₁₅]²⁻与两当量的[AuCl₄]⁻反应制得。它与过量的HBF₄反应，生成[{Co₅C(CO)₁₂}₂Au]⁻。新型衍生物[Co₅C(CO)₁₂(AuPPh₃)]和[Co₅C(CO)₁₁(AuPPh₃)₃]分别是通过与两当量和四当量的[Au(PPh₃)Cl]反应得到的。所有新物种均通过X射线晶体学对其[NEt₄]盐、[NEt₄]盐、[NMe₃(CH₂Ph)]盐以及四氢呋喃·0.5C₆H₁₄溶剂化物进行了结构表征。[Co₅C(CO)₁₂}₂Au]⁻可看作是一种以两个[Co₅C(CO)₁₂]⁻簇合物为配体的均配型Au(i)配合物。类似地，[Co₅C(CO)₁₂(AuPPh₃)]和[Co₅C(CO)₁₁(AuPPh₃)₃]是含有一个[Co₅C(CO)₁₂]⁻簇合物配体以及[Co(CO)₄]⁻或PPh₃的杂配型Au(i)配合物。相反，[Co₅C(CO)₁₁(AuPPh₃)₃]含有由三个[AuPPh₃]⁺片段稳定的[Co₅C(CO)₁₁]³⁻簇合物。[Co₅C(CO)₁₂(AuPPh₃)]和[Co₅C(CO)₁₁(AuPPh₃)₃]已通过电化学和光谱电化学方法在溶液中进行了研究，揭示出其具有形成密切相关的（n = 1 - 3）和（n = 0 - 3）物种的非常丰富的氧化还原倾向。
