Retro-Vinylidene Rearrangements of P- and S-Substituted Ruthenium Vinylidene Complexes

Retro-Vinylidene Rearrangements of P- and S-Substituted Ruthenium Vinylidene Complexes
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P-和S-取代的钌亚乙烯基配合物的逆亚乙烯基重排

DOI:
10.1021/acs.organomet.2c00552
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发表时间:
2023
期刊:
影响因子:
2.8
通讯作者:
and Youichi Ishii
and Youichi Ishii
中科院分区:
化学2区
文献类型:
--
作者:
Takahiro Iwamoto;Kyoka Saito;Takuya Mitsubo;Takuya Kuwabara;and Youichi Ishii

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P-和S-取代的亚乙烯基配合物[Ru{CN C CN C(R)(E)}(dppe)Cp] BArF 4 [E= PO(OMe)2,PO(OEt)2,POPh 2,SPh,和SO 2 Ph],被发现对逆亚乙烯基重排具有活性,从而增加了亚乙烯基/炔异构化可逆体系的新条目。同位素标记实验表明,PO(OMe)2-和POPh 2-取代的配合物通过P-取代基的选择性1,2-迁移发生了逆亚乙烯基重排反应。在SPh取代的配合物中,SPh和R基团在炔/亚乙烯基的可逆异构化反应中均起迁移作用,但SPh基团的迁移仍是主要的反应途径,这些发现将加深对杂原子取代的内炔的炔/亚乙烯基重排机理的理解.
P- and S-substituted vinylidene complexes, [Ru{═C═C(R)(E)}(dppe)Cp]BArF4[E= PO(OMe)2, PO(OEt)2, POPh2, SPh, and SO2Ph], were found to be active for retro-vinylidene rearrangements to add new entries of reversible systems of vinylidene/alkyne isomerization. Isotope labeling experiments revealed that PO(OMe)2- and POPh2-substituted complexes underwent the retro-vinylidene rearrangement via selective 1,2-migration of the P-substituents. In contrast, in the case of a SPh-substituted complex, both the SPh and the R groups served as migrating groups during the reversible alkyne/vinylidene isomerization, though the migration of the SPh group was still the major reaction path. These findings would deepen the mechanistic understanding of alkyne/vinylidene rearrangements of heteroatom-substituted internal alkynes.
P-和S-取代基选择性1,2-迁移生成的亚乙烯基钌配合物:合成、结构和分子内CH·O氢键产生的二色性
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发表时间: 2011-07
期刊: Organometallics
影响因子: 2.8
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