Fluxional processes in diamagnetic and paramagnetic allyl dicarbonyl and 2-methylallyl dicarbonyl molybdenum histidinato complexes as revealed by spectroscopic data and density functional calculations

Chemistry : a European Journal
Dave R van StaverenNils Metzler-Nolte

Abstract

This work describes a detailed study on the structure and dynamics of pseudooctahedral low-valent complexes of the type [Mo(His-N(epsilon)-R)(eta-2-R'-allyl)(CO)(2)] (His=N(delta),N,O-L-histidinate; R=H, R'=H (1); R=C(2)H(4)CO(2)Me, R'=H (2); R=H, R'=Me (3); R=C(2)H(4)CO(2)Me, R'=Me (4)). These diamagnetic 18-electron complexes were comprehensively characterized spectroscopically and by X-ray crystallography. In the solid state, the (substituted) allyl ligand is in an endo position in all compounds, but it is trans to the His-N(delta) atom in 1 and 2, whereas it is trans to the carboxylate O atom for the 2-Me-allyl compounds 3 and 4. In solution, both isomers are present in a solvent-dependent equilibrium. The third isomer (allyl trans to His-NH(2)) is not spectroscopically observed in solution. This is in agreement with the results from density functional (DFT) computations (BPW 91 functional) for 1 and 3, which predict a considerably higher energy (+6.3 and +5.9 kJ mol(-1), respectively) for this isomer. A likely path for isomerization is calculated, which is consistent with the activation energy determined by variable temperature NMR measurements. At least for 3, the preferred path involves several intermediates and a rotati...Continue Reading

References

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Citations

Feb 24, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Julio PérezDaniel Miguel
Aug 8, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Celedonio M AlvarezDaniel Miguel
Sep 11, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·M Dolores Santa MaríaJosé Elguero
Mar 24, 2009·Physical Chemistry Chemical Physics : PCCP·Jane EstephaneAdriano Zecchina
Feb 17, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Raúl García-Rodríguez, Daniel Miguel
Nov 23, 2006·Journal of the American Chemical Society·Thomas L MindtRoger Schibli

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