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摘要
En 中文
The sigma-stannyl complexes [M(SnnBu3)(CO)n(eta 5-C5H5)] (n = 3, M = Mo, W; n = 2, M = Fe) serve as mild reagents for the installation of sigma-arsolyl ligands in transmetallation reactions with As-chloro-arsoles ClAsC4R4 (R = Me, Ph) to afford [M(sigma-AsC4R4)(CO)n(eta 5-C5H5)]. The reaction of [Cr(SnnBu3)(CO)3(eta 5-C5H5)] with ClAsC4Ph4 most likely proceeds in a similar manner but is immediately followed by rapid formation of (AsC4Ph4)2 and [Cr2(CO)6(eta 5-C5H5)2]. The reaction of [Mo(SnnBu3)(CO)3(eta 5-C5H5)] with ClAsC4(SiMe3)-2,5-Me2-3,4 is accompanied by monodesilylation to afford [Mo{sigma-AsC4(SiMe3)-2-Me2-3,4}(CO)3(eta 5-C5H5)]. The slow reaction of [Fe(SnnBu3)(CO)2(eta 5-C5H5)] with ClAsC4Me4 produced only traces of [Fe(sigma-AsC4Me4)(CO)2(eta 5-C5H5)] due to competition with the Diels-Alder type dimerisation of the haloarsole. Although attempts to decarbonylate the sigma-arsolyl complexes were unsuccessful, computational analysis suggests that the trigonal 'XL' arsolenium coordination mode is viable. Mononuclear-sigma-arsolyl complexes of molybdenum, tungsten and iron have been prepared via facile transmetallation from tin, allowing their structural characterisation for the first time.
Keyword:
ASYMMETRIC CYCLOADDITION REACTION
METAL SUBSTITUTED PHOSPHANES
TRANSITION-METAL
CRYSTAL-STRUCTURE
ORGANOMETALLIC COMPOUNDS
PERTURBATION-THEORY
PRACTICAL SYNTHESIS
MOLYBDENUM
BONDS
REACTIVITY
期刊
IF:
3.3
论文数:
3.3W
被引数:
7.7W
机构
引用论文
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