Siloxide Podand Ligand as a Scaffold for Molybdenum-Catalyzed Alkyne Metathesis and Isolation of a Dynamic Metallatetrahedrane Intermediate

Siloxide Podand Ligand as a Scaffold for Molybdenum-Catalyzed Alkyne Metathesis and Isolation of a Dynamic Metallatetrahedrane Intermediate
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二氧化硅荚配体作为钼催化炔复分解的支架以及动态金属四面体中间体的分离

DOI:
10.1021/acs.organomet.9b00430
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发表时间:
2019
期刊:
影响因子:
2.8
通讯作者:
Lee, Semin
Lee, Semin
中科院分区:
化学2区
文献类型:
--
作者:
Thompson, Richard R.;Rotella, Madeline E.;Du, Pu;Zhou, Xin;Fronczek, Frank R.;Kumar, Revati;Gutierrez, Osvaldo;Lee, Semin

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三苯基硅氧是钼(VI)-炔复分解催化剂最成功的辅助配体之一。提出了柔性硅氧配体允许Mo-O-Si键角调节Mo/C的亲电性,从而促进催化。通过引入硅氧氧配体,研究了配体的柔性和Mo-O-Si角对Mo/C的亲电性的影响。它还允许隔离的稀有金属四面体的钼(VI),这被发现是动态的溶液中。
Triphenylsiloxide is one of the most successful ancillary ligands for Mo(VI)-alkyne metathesis catalysts. It was proposed that flexible siloxide ligands allow Mo–O–Si bond angles to modulate the electrophilicity of Mo≡C and thereby promote the catalysis. Introduction of a siloxide podand ligand allowed elucidation of the effect of ligand flexibility and Mo–O–Si angles on the electrophilicity of Mo≡C. It also allowed for the isolation of a rare metallatetrahedrane of Mo(VI) which was found to be dynamic in solution.
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