Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan.
Research Center for Materials Science (RCMS) & Integrated Research Consortium on Chemical Sciences (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan.
Chemistry. 2018 Nov 16;24(64):17138-17147. doi: 10.1002/chem.201804083. Epub 2018 Oct 31.
A synthetic protocol was developed for a series of cubane-type [Mo S M] clusters that incorporate halides of first-row transition metals (M) from Groups 4-10. This protocol is based on the anionic cluster platform [Cp* Mo S ] ([1] ; Cp*=η -C Me ), which crystallizes when K(18-crown-6) is used as the counter cation. Treatment of in situ-generated [1] with such transition-metal halides led to the formation of [Mo S M] clusters, in which the M/halide ratio gradually changes from 1:2 to 1:1.5 and to 1:1, when moving from early to late transition metals. This trend suggests a tendency for early transition metals to tolerate higher oxidation states and adopt larger ionic radii relative to late transition metals. The properties of the [Mo S Fe] cluster 6 a were investigated in detail by using Fe Mössbauer spectroscopy and computational methods.
开发了一种合成方案，用于一系列包含来自第 4-10 族的过渡金属（M）卤化物的笼型[Mo S M]簇合物。该方案基于阴离子簇平台[Cp* Mo S ]([1]；Cp*=η -C Me )，当使用 K(18-冠-6)作为抗衡阳离子时，其会结晶。用这种过渡金属卤化物处理原位生成的[1]，导致[Mo S M]簇合物的形成，其中当从早期过渡金属移动到晚期过渡金属时，M/卤化物的比例逐渐从 1:2 变为 1:1.5，再变为 1:1。这种趋势表明早期过渡金属倾向于容忍更高的氧化态，并相对于晚期过渡金属采用更大的离子半径。通过使用 Fe Mössbauer 光谱和计算方法详细研究了[Mo S Fe]簇合物 6a 的性质。
