σ-胂络合物的亲电胂官能化。

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2024-07-03 DOI:10.1039/D4DT01371A

Ryan M. Kirk and Anthony F. Hill

引用次数: 0

摘要

σ-胂络合物[Mo(AsC4Me4)(CO)3(η5-C5H5)]被 MeOTf 在砷处烷基化，得到五甲基胂络合物[Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf)，而碘甲烷得到[Me2AsC4Me4]I、[MoMe(CO)3(η5-C5H5)]的混合物、[MoI(CO)3(η5-C5H5)]以及顺式和反式[MoI(MeAsC4Me4)(CO)2(η5-C5H5)]和反式[Mo{C(O)Me}(MeAsC4Me4)(CO)2(η5-C5H5)]的芳基络合物、Mo(MeAsC4Me4)(CO)3(η5-C5H5)](OTf)中的芳基配体很容易被丙酮中的 NaI 解离，从而得到游离的 MeAsC4Me4 和 [MoI(CO)3(η5-C5H5)]。类似地，[Mo(AsC4Ph4)(CO)3(η5-C5H5)] 与 MeI 反应生成 MeAsC4Ph4 和 [MoI(CO)3(η5-C5H5)]、而[Mo{AsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)]与 MeOTf 反应生成[Mo{MeAsC4(SiMe3)-2-Me2-3,4}(CO)3(η5-C5H5)](OTf)。Mo(AsC4Me4)(CO)3(η5-C5H5)]与活化炔（RCCR：R = CF3，CO2Me）的反应不是通过[4 + 2]环加成进行的，而是在砷处发生亲电攻击，然后在螺环配合物[Mo{As(C4Me4)CRCRCO}(CO)2(η5-C5H5)]中加入羰基配体进行金属化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Electrophilic As-functionalisation of σ-arsolido complexes†

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Electrophilic As-functionalisation of σ-arsolido complexes†

The σ-arsolido complex [Mo(AsC₄Me₄)(CO)₃(η⁵-C₅H₅)] is alkylated at arsenic by MeOTf to afford the pentamethylarsole complex [Mo(MeAsC₄Me₄)(CO)₃(η⁵-C₅H₅)](OTf) while iodomethane affords a mixture of [Me₂AsC₄Me₄]I, [MoMe(CO)₃(η⁵-C₅H₅)], [MoI(CO)₃(η⁵-C₅H₅)] and the arsole complexes cisoid- and transoid-[MoI(MeAsC₄Me₄)(CO)₂(η⁵-C₅H₅)] and transoid-[Mo{C(O)Me}(MeAsC₄Me₄)(CO)₂(η⁵-C₅H₅)], The arsole ligand in [Mo(MeAsC₄Me₄)(CO)₃(η⁵-C₅H₅)](OTf) is readily liberated by NaI in acetone to afford free MeAsC₄Me₄ and [MoI(CO)₃(η⁵-C₅H₅)]. In a similar manner, the reaction of [Mo(AsC₄Ph₄)(CO)₃(η⁵-C₅H₅)] with MeI affords MeAsC₄Ph₄ and [MoI(CO)₃(η⁵-C₅H₅)], while [Mo{AsC₄(SiMe₃)-2-Me₂-3,4}(CO)₃(η⁵-C₅H₅)] with MeOTf affords [Mo{MeAsC₄(SiMe₃)-2-Me₂-3,4}(CO)₃(η⁵-C₅H₅)](OTf). The reaction of [Mo(AsC₄Me₄)(CO)₃(η⁵-C₅H₅)] with activated alkynes (RCCR: R = CF₃, CO₂Me) does not proceed via [4 + 2] cyclo-addition but rather electrophilic attack at arsenic followed by metallacyclisation with incorporation of a carbonyl ligand in the spirocyclic complexes [Mo{As(C₄Me₄)CRCRCO}(CO)₂(η⁵-C₅H₅)].

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.