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Azavinylidene Complexes from Coupling Reactions of Organonitriles with Phosphines
Organometallics ( IF 2.5 ) Pub Date : 2021-01-20 , DOI: 10.1021/acs.organomet.0c00704 Kui-Fun Lee 1 , Tilong Yang 1 , Long-Yiu Tsang 1 , Herman H. Y. Sung 1 , Ian D. Williams 1 , Zhenyang Lin 1 , Guochen Jia 1
Organometallics ( IF 2.5 ) Pub Date : 2021-01-20 , DOI: 10.1021/acs.organomet.0c00704 Kui-Fun Lee 1 , Tilong Yang 1 , Long-Yiu Tsang 1 , Herman H. Y. Sung 1 , Ian D. Williams 1 , Zhenyang Lin 1 , Guochen Jia 1
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The reactions of the rhenium(III)-phosphine complex ReCl3(PMePh2)3 with organonitriles (NCR) were studied and found to give novel addition as well as simple substitution products. Refluxing ReCl3(PMePh2)3 in acetonitrile (MeCN) yielded a mixture of the organonitrile rhenium complex ReCl3(PMePh2)2(NCMe) and the rhenium phosphonium-substituted azavinylidene complex ReCl3(PMePh2)2{═N═C(PMePh2)Me}. Similarly, reactions of ReCl3(PMePh2)3 with arylnitriles p-R-C6H4CN (R = H, Me, and Br) gave the corresponding azavinylidene complexes ReCl3(PMePh2)2{═N═C(PMePh2)(p-C6H4R)}. The nitrile complex ReCl3(PPh3)2(NCPh) is unreactive toward external PPh3, but it reacts with excess PMe3 to produce the azavinylidene complex ReCl3(PMe3)2{═N═C(PMe3)Ph}. Computational studies reveal the effect of ligand and substituent of organonitriles on the thermodynamics and kinetics for the reactions of ReCl3(PR3)2(NCR′) with PR3. Both the experimental and computational results indicate that nucleophilic addition of phosphines to coordinated nitriles is more favorable for nitriles with an electron-withdrawing group and for phosphines which are more electron-donating.
中文翻译：
有机腈与膦偶联反应的氮杂亚乙烯基配合物
the（III）-膦配合物ReCl 3（PMePh 2）3与有机腈（NCR）的反应进行了研究，发现它可以提供新颖的加成以及简单的取代产物。将ReCl 3（PMePh 2）3回流到乙腈（MeCN）中，得到有机腈rh络合物ReCl 3（PMePh 2）2（NCMe）和rh取代的氮杂亚乙烯基complex ReCl 3（PMePh 2）2（═N═ ）的混合物C（PMePh 2）Me}。同样，ReCl 3（PMePh 2）3的反应用芳基腈p -RC 6 H 4 CN（R = H，Me和Br）得到相应的氮杂亚乙烯基配合物ReCl 3（PMePh 2）2 {═N═C（PMePh 2）（p -C 6 H 4 R）} 。腈络合物ReCl 3（PPh 3）2（NCPh）对外部PPh 3不反应，但与过量的PMe 3反应生成氮杂亚乙烯基络合物ReCl 3（PMe 3）2 {═N═C（PMe 3）Ph}。计算研究表明有机腈的配体和取代基对ReCl 3（PR 3）2（NCR'）与PR 3反应的热力学和动力学的影响。实验和计算结果均表明，将膦类化合物以亲核方式加成到腈中对于具有吸电子基团的腈和更给电子的膦是更有利的。
更新日期：2021-02-08
中文翻译：
有机腈与膦偶联反应的氮杂亚乙烯基配合物
the（III）-膦配合物ReCl 3（PMePh 2）3与有机腈（NCR）的反应进行了研究，发现它可以提供新颖的加成以及简单的取代产物。将ReCl 3（PMePh 2）3回流到乙腈（MeCN）中，得到有机腈rh络合物ReCl 3（PMePh 2）2（NCMe）和rh取代的氮杂亚乙烯基complex ReCl 3（PMePh 2）2（═N═ ）的混合物C（PMePh 2）Me}。同样，ReCl 3（PMePh 2）3的反应用芳基腈p -RC 6 H 4 CN（R = H，Me和Br）得到相应的氮杂亚乙烯基配合物ReCl 3（PMePh 2）2 {═N═C（PMePh 2）（p -C 6 H 4 R）} 。腈络合物ReCl 3（PPh 3）2（NCPh）对外部PPh 3不反应，但与过量的PMe 3反应生成氮杂亚乙烯基络合物ReCl 3（PMe 3）2 {═N═C（PMe 3）Ph}。计算研究表明有机腈的配体和取代基对ReCl 3（PR 3）2（NCR'）与PR 3反应的热力学和动力学的影响。实验和计算结果均表明，将膦类化合物以亲核方式加成到腈中对于具有吸电子基团的腈和更给电子的膦是更有利的。
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