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Carbonylchromium Derivatives of Bismuth: New Syntheses and Relevance to CO Activation
Author(s) -
Shieh Minghuey,
Cherng JiannJang,
Lai YunWen,
Ueng ChuenHer,
Peng ShieMing,
Liu YiHung
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20021004)8:19<4522::aid-chem4522>3.0.co;2-7
Subject(s) - bismuth , chemistry , alkyl , atom (system on chip) , medicinal chemistry , crystallography , stereochemistry , inorganic chemistry , organic chemistry , computer science , embedded system
We have discovered a series of novel pentacarbonylchromium derivatives of bismuth from the reactions of NaBiO 3 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 CO activation of MeOH. Further reactions of 1 with CH 2 Cl 2 or CHCCH 2 Br 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− .