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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U2 - 10.1021/ic101118y
DO - 10.1021/ic101118y
M3 - Article
C2 - 20681628
AN - SCOPUS:77956215127
VL - 49
SP - 8056
EP - 8066
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 17
ER -