Loera Fernandez Ismael I, Donaldson Samantha L, Schipper Desmond E, Andleeb Sohaila, Whitmire Kenton H
Chemistry Department, Rice University , 6100 Main St. MS-60, Houston, Texas 77005, United States.
Inorg Chem. 2016 Nov 7;55(21):11560-11569. doi: 10.1021/acs.inorgchem.6b02092. Epub 2016 Oct 14.
Six new anionic bismuth-oxido clusters containing trifluoroacetate ligands were prepared. These include two new BiO clusters: [M(NCMe)(HO)][Bi(μ-O)(μ-OH)(CFCO)] with an octahedral BiO(OH) core (M = Ni, 1a; Co, 1b) and four BiO clusters, {[Co(NCMe)][Bi(μ-O)(CFCO)]} (2a), {[Co{HC(MeCO)(MeCNH)}][Bi(μ-O)(CFCO)]·2[CFCO]·2[CFCOH]·2[HO]} (2b), {[Cu(NCMe)][Bi(μ-O)(CFCO)]·2[CFCOH]} (2c), and {[MeN][Bi(μ-O)(CFCO)]·2[CFCOH]} (2d). These are among the first bismuth-oxido anionic clusters synthesized, and the first to have transition metal countercations. The BiO anion in 1a and 1b is a high-symmetry octahedron. Additionally, two of the new BiO clusters are arranged in 1D polymeric structures via bridging carboxylate ligands. The cation in compound 2c had not been previously characterized and was also observed in the synthesis of [Co{HC(MeCO)(MeCNH)}][Bi(NO)] (3). The new compounds were characterized using single crystal X-ray crystallography and elemental analysis.
制备了六种含有三氟乙酸酯配体的新型阴离子铋氧化物簇合物。其中包括两种新型BiO簇合物：具有八面体BiO(OH)核的[M(NCMe)(HO)][Bi(μ-O)(μ-OH)(CFCO)]（M = Ni，1a；Co，1b），以及四种BiO簇合物，{[Co(NCMe)][Bi(μ-O)(CFCO)]}（2a）、{[Co{HC(MeCO)(MeCNH)}][Bi(μ-O)(CFCO)]·2[CFCO]·2[CFCOH]·2[HO]}（2b）、{[Cu(NCMe)][Bi(μ-O)(CFCO)]·2[CFCOH]}（2c）和{[MeN][Bi(μ-O)(CFCO)]·2[CFCOH]}（2d）。这些是最早合成的铋氧化物阴离子簇合物之一，也是首批具有过渡金属抗衡阳离子的簇合物。1a和1b中的BiO阴离子是高对称性八面体。此外，两种新型BiO簇合物通过桥连羧酸根配体排列成一维聚合物结构。化合物2c中的阳离子此前未被表征，在[Co{HC(MeCO)(MeCNH)}][Bi(NO)]（3）的合成中也有观察到。使用单晶X射线晶体学和元素分析对新化合物进行了表征。
