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Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes

The chemistry of rare-earth carbene and alkylidene complexes including their synthesis, structure and reaction is a challenging issue because of their high reactivity (or instability) and the lack of synthetic methods. In this work, we report the first synthesis of the bridged bis-alkylidene complex...

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Autores principales: Ma, Wangyang, Yu, Chao, Chi, Yue, Chen, Tianyang, Wang, Lianjun, Yin, Jianhao, Wei, Baosheng, Xu, Ling, Zhang, Wen-Xiong, Xi, Zhenfeng
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5632790/
https://www.ncbi.nlm.nih.gov/pubmed/29147510
http://dx.doi.org/10.1039/c7sc02018j
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author Ma, Wangyang
Yu, Chao
Chi, Yue
Chen, Tianyang
Wang, Lianjun
Yin, Jianhao
Wei, Baosheng
Xu, Ling
Zhang, Wen-Xiong
Xi, Zhenfeng
author_facet Ma, Wangyang
Yu, Chao
Chi, Yue
Chen, Tianyang
Wang, Lianjun
Yin, Jianhao
Wei, Baosheng
Xu, Ling
Zhang, Wen-Xiong
Xi, Zhenfeng
author_sort Ma, Wangyang
collection PubMed
description The chemistry of rare-earth carbene and alkylidene complexes including their synthesis, structure and reaction is a challenging issue because of their high reactivity (or instability) and the lack of synthetic methods. In this work, we report the first synthesis of the bridged bis-alkylidene complexes which feature a 2-butene-1,1,4,4-tetraanion and four Sc–C(sp(3)) bonds by the reaction of 1,4-dilithio-1,3-butadienes with ScCl(3). This reaction proceeds via two key intermediates: an isolable scandacyclopentadiene and a proposed scandacyclopropene. The scandacyclopentadiene undergoes β,β′-C–C bond cleavage to generate the scandacyclopropene, which then dimerizes to afford the bridged bis-alkylidene complex via a cooperative double metathesis reaction. Reaction chemistry study of the bridged bis-alkylidene complex reveals their ligand-based reduction reactivity towards different oxidants such as hexachloroethane, disulfide and cyclooctatetraene.
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spelling pubmed-56327902017-11-16 Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes Ma, Wangyang Yu, Chao Chi, Yue Chen, Tianyang Wang, Lianjun Yin, Jianhao Wei, Baosheng Xu, Ling Zhang, Wen-Xiong Xi, Zhenfeng Chem Sci Chemistry The chemistry of rare-earth carbene and alkylidene complexes including their synthesis, structure and reaction is a challenging issue because of their high reactivity (or instability) and the lack of synthetic methods. In this work, we report the first synthesis of the bridged bis-alkylidene complexes which feature a 2-butene-1,1,4,4-tetraanion and four Sc–C(sp(3)) bonds by the reaction of 1,4-dilithio-1,3-butadienes with ScCl(3). This reaction proceeds via two key intermediates: an isolable scandacyclopentadiene and a proposed scandacyclopropene. The scandacyclopentadiene undergoes β,β′-C–C bond cleavage to generate the scandacyclopropene, which then dimerizes to afford the bridged bis-alkylidene complex via a cooperative double metathesis reaction. Reaction chemistry study of the bridged bis-alkylidene complex reveals their ligand-based reduction reactivity towards different oxidants such as hexachloroethane, disulfide and cyclooctatetraene. Royal Society of Chemistry 2017-10-01 2017-07-13 /pmc/articles/PMC5632790/ /pubmed/29147510 http://dx.doi.org/10.1039/c7sc02018j Text en This journal is © The Royal Society of Chemistry 2017 https://creativecommons.org/licenses/by/3.0/This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/ (https://creativecommons.org/licenses/by/3.0/) ) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Ma, Wangyang
Yu, Chao
Chi, Yue
Chen, Tianyang
Wang, Lianjun
Yin, Jianhao
Wei, Baosheng
Xu, Ling
Zhang, Wen-Xiong
Xi, Zhenfeng
Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes
title Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes
title_full Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes
title_fullStr Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes
title_full_unstemmed Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes
title_short Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes
title_sort formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5632790/
https://www.ncbi.nlm.nih.gov/pubmed/29147510
http://dx.doi.org/10.1039/c7sc02018j
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