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Synthesis, spatial and electronic structure of 1-(+)-neomenthyl-1,2-diphosphole and 1-(+)-neomenthyl-1,2,4-triphosphole tungstenpentacarbonyl complexes.

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Title: Synthesis, spatial and electronic structure of 1-(+)-neomenthyl-1,2-diphosphole and 1-(+)-neomenthyl-1,2,4-triphosphole tungstenpentacarbonyl complexes.
Authors: Zagidullin, Almaz1 zagidullin@iopc.ru, Oshchepkova, Elena1, Burganov, Timur1, Miluykov, Vasili1, Katsyuba, Sergey1, Sinyashin, Oleg1, Lönnecke, Peter2, Hey-Hawkins, Evamarie2
Source: Journal of Organometallic Chemistry. Jul2018, Vol. 867, p125-132. 8p.
Subjects: Chemical synthesis, Raman spectra, Absorption spectra, Carbonyl compounds, Tungsten
Abstract: 3,4,5-Triphenyl-1-(+)-neomenthyl-1,2-diphosphole and 3,5-di-( tert -butyl)-1-(+)-neomenthyl-1,2,4-triphosphole were obtained by alkylation of sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide and 3,5-di-( tert -butyl)-1,2,4-triphosphacyclopentadienide with (−)-menthyl tosylate in 70% yield. These P -heterocycles react with [W(CO) 5 (THF)] to give the 1:1 complexes with high regioselectivity - tungsten is coordinated exclusively by the dicoordinated phosphorus atom P 2 . Complex formation causes quite pronounced charge redistribution within the heterocyclic moieties and has also a rather pronounced impact on the frontier molecular orbitals of the ligands. This is reflected in a strong bathochromic shift of the lowest-energy absorption band and in a change of the corresponding electronic transition from a π-π* transition for the ligands to a metal-to-ligand charge transfer transition (MLCT) for the tungsten complexes. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:3,4,5-Triphenyl-1-(+)-neomenthyl-1,2-diphosphole and 3,5-di-( tert -butyl)-1-(+)-neomenthyl-1,2,4-triphosphole were obtained by alkylation of sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide and 3,5-di-( tert -butyl)-1,2,4-triphosphacyclopentadienide with (−)-menthyl tosylate in 70% yield. These P -heterocycles react with [W(CO) 5 (THF)] to give the 1:1 complexes with high regioselectivity - tungsten is coordinated exclusively by the dicoordinated phosphorus atom P 2 . Complex formation causes quite pronounced charge redistribution within the heterocyclic moieties and has also a rather pronounced impact on the frontier molecular orbitals of the ligands. This is reflected in a strong bathochromic shift of the lowest-energy absorption band and in a change of the corresponding electronic transition from a π-π* transition for the ligands to a metal-to-ligand charge transfer transition (MLCT) for the tungsten complexes. [ABSTRACT FROM AUTHOR]
ISSN:0022328X
DOI:10.1016/j.jorganchem.2017.10.007