Manganese Containing Heterometallic Clusters Containing Ligands Derived from Elements of Groups 15 and 16

Mathur, P. C.; Chatterjee, Saurav; Torubaev, Yu. V.

doi:10.1007/s10876-007-0143-8

Cited by 15 publications

(1 citation statement)

References 58 publications

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“…Previous studies reported that group 11 metal cations could be incorporated into Mn-containing complexes by metal−metal interactions . In addition, although the insertion of metal fragments into the sulfur−sulfur bond of metal carbonyl disulfide clusters has been widely investigated, the related diselenide complexes were less explored . Therefore, we treated the diselenide-containing manganese carbonyl clusters 3 and 4 with [Cu(MeCN) 4 ][BF 4 ] or Mn(CO) 5 Br.…”

Section: Resultsmentioning

confidence: 99%

Selenium−Manganese Carbonyl Clusters: Synthesis, Reversible Transformation, Electrochemical Properties, and Theoretical Calculations

Chu

Lin

et al. 2010

Organometallics

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The reaction of Se8 with 6 equiv of Mn2(CO)10 in concentrated KOH/MeOH solutions led to the formation of the odd-electron cluster [Se2Mn3(CO)9]2− (1), which was oxidized with [Cu(MeCN)4][BF4] to give the oxidation product [Se2Mn3(CO)9]− (2). Cluster 2 could be reconverted into cluster 1 by the addition of 4 M KOH/MeOH solutions in MeCN. While the trigonal-bipyramidal cluster 2 underwent cluster expansion to give rise to the large Se-inserted cluster [Se6Mn6(CO)18]4− (3) upon the reaction with a 1/8 equiv of Se8 in KOH/MeOH solutions, the square-pyramidal cluster 1 was transformed into the even larger Se-rich cluster [Se10Mn6(CO)18]4− (4) upon the addition of a 3/8 equiv of Se8 in MeOH. Cluster 3 underwent cluster expansion to form cluster 4 when treated with an additional 1/2 equiv of Se8 in MeCN. Conversely, cluster 4 was selectively reconverted into cluster 1 or 3 upon treatment with 4 or 2 equiv of Mn2(CO)10 in KOH/MeOH solutions, respectively. On the other hand, the Se6Mn6 cluster 3 was transformed into cluster 1 when treated with 2 equiv of Mn2(CO)10 in KOH/MeOH solutions. Furthermore, when cluster 3 was treated with [Cu(MeCN)4][BF4] or Mn(CO)5Br, cluster 2 and/or [Se5Mn4(CO)12]2− (5) were obtained. X-ray analysis showed that cluster 5 consisted of four Mn(CO)3 fragments, which were further connected by one μ3-Se and two μ3- and μ4-Se2 moieties to give a nest-like cluster. Moreover, Se10Mn6 cluster 4 could also be transformed into cluster 5 upon reaction with [Cu(MeCN)4][BF4] or Mn(CO)5Br. After a long reaction time, a new picnic-basket-like cluster, [Se4Mn3(CO)10]− (6), formed, which was also obtained from cluster 5 with [Cu(MeCN)4][BF4] or Mn(CO)5Br. Furthermore, the nature, cluster transformation and interconversion, and electrochemical properties of these Se−Mn−CO clusters were elucidated by molecular calculations at the B3PW91 level of the density functional theory.

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Section: Resultsmentioning

confidence: 99%

Selenium−Manganese Carbonyl Clusters: Synthesis, Reversible Transformation, Electrochemical Properties, and Theoretical Calculations

Chu

Lin

et al. 2010

Organometallics

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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

Shieh

Chu

et al. 2013

Chemistry An Asian Journal

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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, [E2CrMn2(CO)9](2-) (E=S, 1; Se, 2). Clusters 1 and 2 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, [Te2CrMn2(CO)9](2-) (3), was obtained from the ring-closure of Te2Mn2 ring complex [Te2Mn2Cr2(CO)18](2-) (4). Upon bubbling with CO, clusters 2 and 3 were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10](2-) (E=Se, 5; Te, 6), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster 6 was paramagnetic, with S=1 at room temperature; however, the Se analogue (5) was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster 6 could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn2(CO)11](2-) (7). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations.

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ChemInform Abstract: Manganese‐Containing Heterometallic Clusters with Ligands Derived from Elements of Groups 15 and 16

Mathur¹,

Chatterjee²,

Torubaev³

2009

ChemInform

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Manganese Containing Heterometallic Clusters Containing Ligands Derived from Elements of Groups 15 and 16

Cited by 15 publications

References 58 publications

Selenium−Manganese Carbonyl Clusters: Synthesis, Reversible Transformation, Electrochemical Properties, and Theoretical Calculations

Selenium−Manganese Carbonyl Clusters: Synthesis, Reversible Transformation, Electrochemical Properties, and Theoretical Calculations

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

ChemInform Abstract: Manganese‐Containing Heterometallic Clusters with Ligands Derived from Elements of Groups 15 and 16

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Manganese Containing Heterometallic Clusters Containing Ligands Derived from Elements of Groups 15 and 16

Cited by 15 publications

References 58 publications

Selenium−Manganese Carbonyl Clusters: Synthesis, Reversible Transformation, Electrochemical Properties, and Theoretical Calculations

Selenium−Manganese Carbonyl Clusters: Synthesis, Reversible Transformation, Electrochemical Properties, and Theoretical Calculations

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

ChemInform Abstract: Manganese‐Containing Heterometallic Clusters with Ligands Derived from Elements of Groups 15 and 16

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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