TY - JOUR
T1 - Carbonylchromium derivatives of bismuth
T2 - New syntheses and relevance to C-O activation
AU - Shieh, Minghuey
AU - Cherng, Jiann Jang
AU - Lai, Yun Wen
AU - Ueng, Chuen Her
AU - Peng, Shie Ming
AU - Liu, Yi Hung
PY - 2002/10/4
Y1 - 2002/10/4
N2 - We have discovered a series of novel pentacarbonylchromium derivatives of bismuth from the reactions of NaBiO3 with [Cr(CO)6] in KOH/MeOH solutions. When the reaction was carried out at room temperature, the highly charged [Bi{Cr(CO)5}4]3- (1) was obtained, whose structure was shown by X-ray analysis to possess a central bismuth atom tetrahedrally coordinated to four [Cr(CO)5] groups. As the reaction was heated at 80°C, the methyl-substituted complex [MeBi{Cr(CO)5}3]2-(2) was obtained, presumably via the C-O activation of MeOH. Further reactions of 1 with CH2Cl2 or CH≡CCH2Br form the halo-substituted complexes [XBi{Cr(CO)5}3]2-(X = Cl, 3; Br, 4), respectively. On the other hand, the reactions of 1 with RI (R = Me, Et) led to the formation of the alkyl-substituted complexes [RBi{Cr(CO)5}3]2-(R = Me, 2; Et). The formation of complexes 1-4 is discussed, presumably via the intermediate bismuthinidene [Bi{Cr(CO)5}3]- or the trianion [Bi{Cr(CO)5}3]3-.
AB - We have discovered a series of novel pentacarbonylchromium derivatives of bismuth from the reactions of NaBiO3 with [Cr(CO)6] in KOH/MeOH solutions. When the reaction was carried out at room temperature, the highly charged [Bi{Cr(CO)5}4]3- (1) was obtained, whose structure was shown by X-ray analysis to possess a central bismuth atom tetrahedrally coordinated to four [Cr(CO)5] groups. As the reaction was heated at 80°C, the methyl-substituted complex [MeBi{Cr(CO)5}3]2-(2) was obtained, presumably via the C-O activation of MeOH. Further reactions of 1 with CH2Cl2 or CH≡CCH2Br form the halo-substituted complexes [XBi{Cr(CO)5}3]2-(X = Cl, 3; Br, 4), respectively. On the other hand, the reactions of 1 with RI (R = Me, Et) led to the formation of the alkyl-substituted complexes [RBi{Cr(CO)5}3]2-(R = Me, 2; Et). The formation of complexes 1-4 is discussed, presumably via the intermediate bismuthinidene [Bi{Cr(CO)5}3]- or the trianion [Bi{Cr(CO)5}3]3-.
KW - Bismuth
KW - C-O activation
KW - Carbonyl ligands
KW - Chromium
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U2 - 10.1002/1521-3765(20021004)8:19<4522::AID-CHEM4522>3.0.CO;2-7
DO - 10.1002/1521-3765(20021004)8:19<4522::AID-CHEM4522>3.0.CO;2-7
M3 - Article
C2 - 12355541
AN - SCOPUS:0037020309
VL - 8
SP - 4522
EP - 4527
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 19
ER -