ISSN:
0009-2940
Keywords:
Methylcarbene complexes of chromium and tungsten
;
Cyclohexadienyl tricarbonyliron, carbene derivatives of
;
Cycloheptadienyl tricarbonyliron, carbene derivatives of
;
Cycloheptatrienyl, carbene derivatives of
;
Enol ether, elimination from carbene complexes
;
Spirocyclopropanes, elimination from carbene complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Organic Syntheses via Transition Metal Complexes, 71[1]. - Methylcarbene Complexes of Chromium and Tungsten with Cycloheptatrienyl-, Cyclohexadienyl[Fe(CO)3]- and Cycloheptadienyl[Fe(CO)3] SubstituentsMethylcarbene complexes LnM=C(OEt)CH3 1 [LnM = (CO)5Cr, (CO)5W] react with tropylium tetrafluoroborate (2a) or coordinated olefins of [C6H7Fe(CO)3]BF4 (2c), [C7H9Fe-(CO)3]BF4 (2d), and [C7H7Fe2(CO)6]BF4 (2d) in the presence of Et3N to give complexes LnM=C(OEt)CH2R 3a-e and LnM=C(OEt)CHR2 7a-d by substitution of one or two α-hydrogen atoms. The trimetallic WFe2 carbene complexes 7c, d derived from 1b with 2c, d form three stereoisomers each, which are fully characterized spectroscopically, (R*,R*,S*)-7c additionally also by an X-ray structure analysis, Ligand elimination from 3 and 7 may involve a-and/or β-hydrogen transfer reactions: Thus enol ethers (Z/E)-6 are eliminated from α-monosubstituted methylcarbene complexes 3a, c, d in yields of 62-90% by a pyridine-induced transfer of an α-hydrogen to the carbene carbon atom; with increasing steric demand of R the elimination of the (Z) isomer (Z)-6 from 3 is favoured over the formation of the (E) isomer (E)-6. The enol ether 10 becomes a minor side product in the pyridine-induced ligand elimination from α-disubstituted complexes 7a, b. In these cases the spirocyclopropane 8 is formed as the main product (60-82%) besides the 4,5-homotropylidene 9 by a conformationally directed β-hydrogen transfer reaction.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19941270424
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