A family of rhodium(I) NHC chelates featuring O-containing tethers for catalytic tandem alkene isomerization–hydrosilylation,Dalton Transactions

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A family of rhodium(I) NHC chelates featuring O-containing tethers for catalytic tandem alkene isomerization–hydrosilylation
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-11-18 , DOI: 10.1039/d0dt03698f
Ravi Srivastava _{1,

2,

3,

4,

5} , Martin Jakoobi _{1,

2,

3,

4,

5} , Chloé Thieuleux _{1,

2,

3,

4,

5} , Elsje Alessandra Quadrelli _{1,

2,

3,

4,

5} , Clément Camp _{1,

2,

3,

4,

5}

Affiliation

The rhodium complex Rh(HL)(COD)Cl, 1, L being a functionalized N-heterocyclic carbene (NHC) ligand with an oxygen-containing pendant arm, has been used as the entry point to synthesize a series of neutral and cationic Rh(I) O,C chelates. While the Rh–carbene interaction is similar in all these 16-electron complexes, structural analysis reveals that the strength of the Rh–O bond is greatly affected by the nature of the O-donor: R-O⁻ > R-OH > R-OBF₃. These subtle changes in the nature of the O-containing tether are found to be responsible for large differences in the alkene hydrosilylation catalytic activity of these compounds: the stronger the Rh–O interaction, the better the catalytic performances. The most active catalyst, [Rh(L)(COD)], 2, demonstrated good catalytic activity under mild reaction conditions for the hydrosilylation of a range of alkene substrates with the industrially relevant non-activated tertiary silane, 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD^HM). Furthermore, this complex is an effective catalyst for the selective remote functionalization of internal olefins at room temperature via tandem alkene isomerization–hydrosilylation.

中文翻译：

一族NHC铑（I）螯合物，具有含O的系链，用于催化串联烯烃的异构化-氢化硅烷化

铑配合物Rh（HL）（COD）Cl，1（L是具有含氧侧链的功能化N杂环卡宾（NHC）配体）已用作合成一系列中性和阳离子Rh的入口点（I）O，C螯合物。虽然Rh的卡宾相互作用是在所有这些16电子复合物类似，结构分析表明铑-O键的强度有很大的影响通过O形供体的性质：RO ^- > R-OH> R-OBF ₃。发现这些含O系链性质的细微变化是这些化合物的烯烃氢化硅烷化催化活性差异很大的原因：Rh-O相互作用越强，催化性能越好。活性最高的催化剂[Rh（L）（COD）] 2在温和的反应条件下表现出良好的催化活性，可用于与工业相关的非活化叔硅烷1,1,1， 3,5,5,5-七甲基三硅氧烷（MD ^H M）。此外，该配合物是一种有效的催化剂，可在室温下通过串联烯烃的异构化-氢化硅烷化选择性地对内烯烃进行远程官能化。

更新日期：2020-11-25

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