Trigonal-bipyramidal and square-pyramidal chromium-manganese chalcogenide clusters, [E2CrMn2(CO)n]2- (E=S, Se, Te; N=9, 10): Synthesis, electrochemistry, UV/Vis absorption, and computational studies

Minghuey Shieh*, Chun Hsien Yu, Yen Yi Chu, Yu Wen Guo, Chung Yi Huang, Kai Jieah Hsing, Pei Chi Chen, Chung Feng Lee

*此作品的通信作者

研究成果: 雜誌貢獻期刊論文同行評審

7 引文 斯高帕斯(Scopus)

摘要

The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr-Mn-carbonyl clusters, [E2CrMn 2(CO)9]2- (E=S,; Se,). Clusters and were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te 2CrMn2(CO)9]2- (), was obtained from the ring-closure of Te2Mn2 ring complex [Te 2Mn2Cr2(CO)18]2- (). Upon bubbling with CO, clusters and were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10]2- (E=Se,; Te,), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster was paramagnetic, with S=1 at room temperature; however, the Se analogue () was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn 2(CO)11]2- (). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations. Show and tellurium: Cr-Mn trigonal-bipyramidal clusters, [E2CrMn2(CO) 9]2- (E=S, Se, Te), their carbonylated square-pyramidal (SP) clusters, [E2CrMn2(CO)10]2- (E=Se, Te), and an arachno-cluster, [Te2CrMn2(CO) 11]2-, are reported. The Te SP cluster was an electron-precise paramagnetic species, whilst the Se analogue diamagnetic. DFT calculations were performed to elucidate their formation, electrochemistry, and UV/Vis absorption.

原文英語
頁(從 - 到)963-973
頁數11
期刊Chemistry - An Asian Journal
8
發行號5
DOIs
出版狀態已發佈 - 2013 5月

ASJC Scopus subject areas

  • 生物化學
  • 有機化學

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