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镧（III）上2-磷乙炔硫醇酸根阴离子的η配位和官能化*

η -Coordination and Functionalization of the 2-Phosphaethynthiolate Anion at Lanthanum(III)*.

作者信息

Watt Fabian A, Burkhardt Lukas, Schoch Roland, Mitzinger Stefan, Bauer Matthias, Weigend Florian, Goicoechea Jose M, Tambornino Frank, Hohloch Stephan

机构信息

Department of Chemistry and Center for Sustainable Systems Design (CSSD), Paderborn University, Warburger Strasse 100, 33098, Paderborn, Germany.

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.

出版信息

Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9534-9539. doi: 10.1002/anie.202100559. Epub 2021 Mar 11.

DOI:10.1002/anie.202100559
PMID:33565689
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8252525/
Abstract

We present the η -coordination of the 2-phosphaethynthiolate anion in the complex (PN) La(SCP) (2) [PN=N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide)]. Structural comparison with dinuclear thiocyanate-bridged (PN) La(μ-1,3-SCN) La(PN) (3) and azide-bridged (PN) La(μ-1,3-N ) La(PN) (4) complexes indicates that the [SCP] coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π*-orbital of the [SCP] ligand to the LUMO of complex 2, rendering it the ideal precursor for the first functionalization of the [SCP] anion. Complex 2 was therefore reacted with CAACs which induced a selective rearrangement of the [SCP] ligand to form the first CAAC stabilized group 15-group 16 fulminate-type complexes (PN) La{SPC( CAAC)} (5 a,b, R=Ad, Me). A detailed reaction mechanism for the SCP-to-SPC isomerization is proposed based on DFT calculations.

摘要

我们展示了配合物(PN)La(SCP)(2)[PN = N-(2-(二异丙基膦基)-4-甲基苯基)-2,4,6-三甲基苯胺]中2-磷乙炔硫醇酸根阴离子的η配位。与双核硫氰酸根桥联(PN)La(μ-1,3-SCN)La(PN)(3)和叠氮根桥联(PN)La(μ-1,3-N)La(PN)(4)配合物的结构比较表明，[SCP]配位模式主要受电子因素而非空间因素控制。量子力学研究表明，[SCP]配体的反键π*轨道对配合物2的最低未占分子轨道有很大贡献，使其成为[SCP]阴离子首次功能化的理想前体。因此，配合物2与CAACs反应，诱导[SCP]配体发生选择性重排，形成首个CAAC稳定的第15族-第16族雷酸盐型配合物(PN)La{SPC(CAAC)}(5 a,b，R = Ad, Me)。基于密度泛函理论计算，提出了SCP到SPC异构化的详细反应机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/29d5b52fb4e5/ANIE-60-9534-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/6db738369d24/ANIE-60-9534-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/bad5325535b9/ANIE-60-9534-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/7e54451b4d84/ANIE-60-9534-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/ed1510d09b04/ANIE-60-9534-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/c32a9dcf7961/ANIE-60-9534-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/bc1809d296c8/ANIE-60-9534-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/29d5b52fb4e5/ANIE-60-9534-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/6db738369d24/ANIE-60-9534-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/bad5325535b9/ANIE-60-9534-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/7e54451b4d84/ANIE-60-9534-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/ed1510d09b04/ANIE-60-9534-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/c32a9dcf7961/ANIE-60-9534-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/bc1809d296c8/ANIE-60-9534-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2934/8252525/29d5b52fb4e5/ANIE-60-9534-g001.jpg

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