Synthesis, Structure, and Reactivity of Magnesium Pentalenides

被引：5

作者：

Sanderson, Hugh J. ^{[1
]}

Kociok-Kohn, Gabriele ^{[2
]}

Hintermair, Ulrich ^{[1
,3
]}

机构：

[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England

[2] Univ Bath, Mat & Chem Characterisat Facil, Bath BA2 7AY, Avon, England

[3] Univ Bath, Inst Sustainabil, Bath BA2 7AY, Avon, England

来源：

INORGANIC CHEMISTRY | 2023年 / 62卷 / 39期

关键词：

MAGNETIC-RESONANCE SPECTRA; COMPLEXES; CYCLOOCTATETRAENE; METAL; DERIVATIVES; DIFFRACTION; CHEMISTRY; REAGENTS; DIANION; BARIUM;

D O I：

10.1021/acs.inorgchem.3c02087

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The first magnesium pentalenide complexes have been synthesized via deprotonative metalation of 1,3,4,6-tetraphenyldihydropentalene (Ph(4)PnH(2) ) with magnesium alkyls. Both the nature of the metalating agent and the reaction solvent influenced the structure of the resulting complexes, and an equilibrium between Mg[Ph(4)Pn] and [(BuMg)-Bu-n](2) [Ph(4)Pn] was found to exist and investigated by NMR, XRD, and UV-vis spectroscopic techniques. Studies on the reactivity of Mg[Ph(4)Pn] with water, methyl iodide, and trimethylsilylchloride revealed that the [Ph(4)Pn]( 2-) unit undergoes electrophilic addition at 1,5-positions instead of 1,4-positions known for the unsubstituted pentalenide, Pn(2-), highlighting the electronic influence of the four aryl substituents on the pentalenide core. The ratio of syn/anti addition was found to be dependent on the size of the incoming electrophile, with methylation yielding a 60:40 mixture, while silylation yielded exclusively the anti-isomer.

引用

页码：15983 / 15991

页数：9

共 44 条

[1] MAIN GROUP CONJUGATED ORGANIC ANION CHEMISTRY .1. SYNTHESIS OF MAGNESIUM ANTHRACENE, SILYLATED ANTHRACENES, OR FLUORANTHENE TETRAHYDROFURAN AND TERTIARY AMINE COMPLEXES AND OF MAGNESIUM CYCLOOCTATETRAENE - X-RAY STRUCTURE OF [MGL(TMEDA)].[MGL(THF)2] (L=9,10-BIS(TRIMETHYLSILYL)ANTHRACENE)N [J].