Schulz Jiří, Císařová Ivana, Gyepes Róbert, Štěpnička Petr
Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40, Prague, Czech Republic.
Angew Chem Int Ed Engl. 2021 Mar 22;60(13):6992-6996. doi: 10.1002/anie.202014359. Epub 2021 Feb 17.
Au complexes combining hard oxygen and soft (diphenylphosphanyl)ferrocene (L) ligands in their molecules were synthesized, viz. the gold hydroxides [Au(OH)(L-κP)] (5) and [{Au(L-κP)} (μ-OH)][BF ] (4), and the oxonium cluster [{Au(L-κP)} (μ -O)][BF ] (1). In-situ auration of 1 produced [{Au(L-κP)} (μ -O)][BF ] (2), which spontaneously converted into a dimeric tetragold complex featuring bridging phosphanylferrocenyl groups geminally diaurated in position 2 of the ferrocene scaffold. The same complex and its isomer incorporating ferrocene-1,1'-diyl bridges resulted similarly from 4. Upon crystallization, compound 5 underwent a redox reaction, producing a structurally unique, crown-like, mixed-valent Au /Au cluster, [Au (L-κP) ]OH. Compounds 1 and 5 were used to prepare the analogous, N-bridged complexes, [{Au(L-κP)} (μ -NFc)][BF ] (Fc=ferrocenyl) and [{Au(L-κP)} (μ -N)][BF ]. The compounds were structurally characterized and further studied by DFT calculations.
合成了分子中结合硬氧和软（二苯基膦基）二茂铁（L）配体的金配合物，即氢氧化金[Au(OH)(L-κP)]（5）和[{Au(L-κP)}(μ-OH)][BF₄]（4），以及氧鎓簇[{Au(L-κP)}(μ₂-O)][BF₄]（1）。1的原位金化反应生成[{Au(L-κP)}(μ₂-O)][BF₄]（2），其自发转化为一种二聚体四金配合物，该配合物具有在二茂铁骨架的2位双金化的桥连膦基二茂铁基团。同样的配合物及其包含二茂铁-1,1'-二基桥的异构体也以类似方式由4得到。结晶时，化合物5发生氧化还原反应，生成一种结构独特的冠状混合价Au⁺/Au³⁺簇合物[Au₇(L-κP)₄]OH。化合物1和5用于制备类似的N桥连配合物[{Au(L-κP)}(μ₂-NFc)][BF₄]（Fc = 二茂铁基）和[{Au(L-κP)}(μ₂-N)][BF₄]。通过DFT计算对这些化合物进行了结构表征和进一步研究。
