Chromium-manganese selenide carbonyl complexes: Paramagnetic clusters and relevance to C = O activation of acetone

Minghuey Shieh; Chien Nan Lin; Chia Yeh Miu; Miao Hsing Hsu; Yi Wen Pan; Li Fang Ho

doi:10.1021/ic101118y

Chromium-manganese selenide carbonyl complexes: Paramagnetic clusters and relevance to C = O activation of acetone

Minghuey Shieh^*, Chien Nan Lin, Chia Yeh Miu, Miao Hsing Hsu, Yi Wen Pan, Li Fang Ho

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

The paramagnetic even-electron cluster, [Et₄N] ₂[Se₂Cr₃(CO)₁₀], was found to react readily with Mn(CO)₅Br in acetone to produce two unprecedented mixed chromium-manganese selenide carbonyl complexes, [Et₄N][Me ₂CSe₂{Mn(CO)₄}{Cr(CO)₅} ₂] ([Et₄N][1]) and [Et₄N]₂[Se ₂Mn₃(CO)₁₀{Cr(CO)₅}₂] ([Et₄N]₂[2]). X-ray crystallographic analysis showed that anion 1 consisted of two Se-Cr(CO)₅ moieties, which were further bridged by one isopropylene group and one Mn(CO)₄ moiety. The dianionic cluster 2 was shown to display a Se₂Mn₃ square-pyramidal core with each Se atom externally coordinated by one Cr(CO)₅ group. The formation of complex 1, presumably via C=O activation of acetone, was further facilitated by acidification of the reaction of [Et₄N]₂[Se₂Cr₃(CO)₁₀] with Mn(CO)₅Br in acetone. Complex 1 readily transformed into 2 upon treatment with Mn₂(CO)₁₀ in a KOH/MeOH/MeCN solution. Cluster 2 was a 51-electron species, which readily converted to the known 49-electron cluster [Se₂Mn₃(CO)₉]^2- upon heating and bubbling with CO. Magnetic studies of the even-electron cluster, [Et₄N]₂[Se₂Cr₃(CO) ₁₀], and the odd-electron species, [Et₄N]₂[2] and [PPN]₂[Se₂Mn₃(CO)₉], were determined by the SQUID measurement to have 2, 3, and 1 unpaired electrons, respectively. In addition, the nature and formation of complexes 1 and 2 are discussed, and the magnetic properties and electrochemistry of [Se ₂Cr₃(CO)₁₀]^2-, 2, and [Se ₂Mn₃(CO)₉]^2- were further studied and elucidated by molecular orbital calculations at the PW91 level of density functional theory.

Original language	English
Pages (from-to)	8056-8066
Number of pages	11
Journal	Inorganic Chemistry
Volume	49
Issue number	17
DOIs	https://doi.org/10.1021/ic101118y
Publication status	Published - 2010 Sept 6

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic101118y

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@article{d5c594c4dbf84b7494914d308d735177,

title = "Chromium-manganese selenide carbonyl complexes: Paramagnetic clusters and relevance to C = O activation of acetone",

abstract = "The paramagnetic even-electron cluster, [Et4N] 2[Se2Cr3(CO)10], was found to react readily with Mn(CO)5Br in acetone to produce two unprecedented mixed chromium-manganese selenide carbonyl complexes, [Et4N][Me 2CSe2{Mn(CO)4}{Cr(CO)5} 2] ([Et4N][1]) and [Et4N]2[Se 2Mn3(CO)10{Cr(CO)5}2] ([Et4N]2[2]). X-ray crystallographic analysis showed that anion 1 consisted of two Se-Cr(CO)5 moieties, which were further bridged by one isopropylene group and one Mn(CO)4 moiety. The dianionic cluster 2 was shown to display a Se2Mn3 square-pyramidal core with each Se atom externally coordinated by one Cr(CO)5 group. The formation of complex 1, presumably via C=O activation of acetone, was further facilitated by acidification of the reaction of [Et4N]2[Se2Cr3(CO)10] with Mn(CO)5Br in acetone. Complex 1 readily transformed into 2 upon treatment with Mn2(CO)10 in a KOH/MeOH/MeCN solution. Cluster 2 was a 51-electron species, which readily converted to the known 49-electron cluster [Se2Mn3(CO)9]2- upon heating and bubbling with CO. Magnetic studies of the even-electron cluster, [Et4N]2[Se2Cr3(CO) 10], and the odd-electron species, [Et4N]2[2] and [PPN]2[Se2Mn3(CO)9], were determined by the SQUID measurement to have 2, 3, and 1 unpaired electrons, respectively. In addition, the nature and formation of complexes 1 and 2 are discussed, and the magnetic properties and electrochemistry of [Se 2Cr3(CO)10]2-, 2, and [Se 2Mn3(CO)9]2- were further studied and elucidated by molecular orbital calculations at the PW91 level of density functional theory.",

author = "Minghuey Shieh and Lin, {Chien Nan} and Miu, {Chia Yeh} and Hsu, {Miao Hsing} and Pan, {Yi Wen} and Ho, {Li Fang}",

year = "2010",

month = sep,

day = "6",

doi = "10.1021/ic101118y",

language = "English",

volume = "49",

pages = "8056--8066",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "17",

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TY - JOUR

T1 - Chromium-manganese selenide carbonyl complexes

T2 - Paramagnetic clusters and relevance to C = O activation of acetone

AU - Shieh, Minghuey

AU - Lin, Chien Nan

AU - Miu, Chia Yeh

AU - Hsu, Miao Hsing

AU - Pan, Yi Wen

AU - Ho, Li Fang

PY - 2010/9/6

Y1 - 2010/9/6

N2 - The paramagnetic even-electron cluster, [Et4N] 2[Se2Cr3(CO)10], was found to react readily with Mn(CO)5Br in acetone to produce two unprecedented mixed chromium-manganese selenide carbonyl complexes, [Et4N][Me 2CSe2{Mn(CO)4}{Cr(CO)5} 2] ([Et4N][1]) and [Et4N]2[Se 2Mn3(CO)10{Cr(CO)5}2] ([Et4N]2[2]). X-ray crystallographic analysis showed that anion 1 consisted of two Se-Cr(CO)5 moieties, which were further bridged by one isopropylene group and one Mn(CO)4 moiety. The dianionic cluster 2 was shown to display a Se2Mn3 square-pyramidal core with each Se atom externally coordinated by one Cr(CO)5 group. The formation of complex 1, presumably via C=O activation of acetone, was further facilitated by acidification of the reaction of [Et4N]2[Se2Cr3(CO)10] with Mn(CO)5Br in acetone. Complex 1 readily transformed into 2 upon treatment with Mn2(CO)10 in a KOH/MeOH/MeCN solution. Cluster 2 was a 51-electron species, which readily converted to the known 49-electron cluster [Se2Mn3(CO)9]2- upon heating and bubbling with CO. Magnetic studies of the even-electron cluster, [Et4N]2[Se2Cr3(CO) 10], and the odd-electron species, [Et4N]2[2] and [PPN]2[Se2Mn3(CO)9], were determined by the SQUID measurement to have 2, 3, and 1 unpaired electrons, respectively. In addition, the nature and formation of complexes 1 and 2 are discussed, and the magnetic properties and electrochemistry of [Se 2Cr3(CO)10]2-, 2, and [Se 2Mn3(CO)9]2- were further studied and elucidated by molecular orbital calculations at the PW91 level of density functional theory.

AB - The paramagnetic even-electron cluster, [Et4N] 2[Se2Cr3(CO)10], was found to react readily with Mn(CO)5Br in acetone to produce two unprecedented mixed chromium-manganese selenide carbonyl complexes, [Et4N][Me 2CSe2{Mn(CO)4}{Cr(CO)5} 2] ([Et4N][1]) and [Et4N]2[Se 2Mn3(CO)10{Cr(CO)5}2] ([Et4N]2[2]). X-ray crystallographic analysis showed that anion 1 consisted of two Se-Cr(CO)5 moieties, which were further bridged by one isopropylene group and one Mn(CO)4 moiety. The dianionic cluster 2 was shown to display a Se2Mn3 square-pyramidal core with each Se atom externally coordinated by one Cr(CO)5 group. The formation of complex 1, presumably via C=O activation of acetone, was further facilitated by acidification of the reaction of [Et4N]2[Se2Cr3(CO)10] with Mn(CO)5Br in acetone. Complex 1 readily transformed into 2 upon treatment with Mn2(CO)10 in a KOH/MeOH/MeCN solution. Cluster 2 was a 51-electron species, which readily converted to the known 49-electron cluster [Se2Mn3(CO)9]2- upon heating and bubbling with CO. Magnetic studies of the even-electron cluster, [Et4N]2[Se2Cr3(CO) 10], and the odd-electron species, [Et4N]2[2] and [PPN]2[Se2Mn3(CO)9], were determined by the SQUID measurement to have 2, 3, and 1 unpaired electrons, respectively. In addition, the nature and formation of complexes 1 and 2 are discussed, and the magnetic properties and electrochemistry of [Se 2Cr3(CO)10]2-, 2, and [Se 2Mn3(CO)9]2- were further studied and elucidated by molecular orbital calculations at the PW91 level of density functional theory.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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Chromium-manganese selenide carbonyl complexes: Paramagnetic clusters and relevance to C = O activation of acetone

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CCDC 810412: Experimental Crystal Structure Determination

CCDC 810411: Experimental Crystal Structure Determination

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Chromium-manganese selenide carbonyl complexes: Paramagnetic clusters and relevance to C = O activation of acetone

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CCDC 810412: Experimental Crystal Structure Determination

CCDC 810411: Experimental Crystal Structure Determination

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