Issue 22, 2009

Synthetic analogs for evaluating the influence of N–H⋯S hydrogen bonds on the formation of thioester in acetyl coenzyme a synthase

Abstract

A series of square planar methylnickel(II) complexes, (dppe)Ni(Me)(SAr) (dppe = 1,2-bis(diphenylphosphino)ethane); 2. Ar = phenyl; 3. Ar = pentafluorophenyl; 4. Ar = o-pivaloylaminophenyl; 5. Ar = p-pivaloylaminophenyl; (depe)Ni(Me)(SAr), (depe = 1,2-bis(diethylphosphino)ethane); 7. Ar = phenyl; 8. Ar = pentafluorophenyl; 9. Ar = o-pivaloylaminophenyl; 10. Ar = p-pivaloylaminophenyl), were synthesized via the reaction of (dppe)NiMe2 (1) and (depe)NiMe2 (6) with either the corresponding thiol or disulfide. These complexes were characterized by various spectroscopic methods including 31P NMR, 1H NMR, 13C NMR and infrared spectroscopies and in most cases by X-ray diffraction analyses. Solid state and solution measurements establish that 4 and 9 contain intramolecular N–H⋯S bonds. Carbonylation of the complexes 2–4, 7–10 leads to (dRpe)Ni(CO)2 and MeC(O)SArvia the intermediacy of the acylnickel adducts, (dRpe)Ni(C(O)Me)(SAr), detected at low temperature by 31P NMR spectroscopy. Consistent with experimental observations, density functional theory results reveal that the intramolecular hydrogen bond in 9 stabilizes the acylnickel adduct compared with its non-hydrogen-bonded adduct, 10. Oxidative addition of MeC(O)SC6F5 to (dRpe)Ni(COD) followed by spontaneous decarbonylation proceeds in variable yields generating 3 and 8.

Graphical abstract: Synthetic analogs for evaluating the influence of N–H⋯S hydrogen bonds on the formation of thioester in acetyl coenzyme a synthase

Supplementary files

Article information

Article type
Paper
Submitted
26 Jan 2009
Accepted
08 Apr 2009
First published
27 Apr 2009

Dalton Trans., 2009, 4359-4369

Synthetic analogs for evaluating the influence of N–H⋯S hydrogen bonds on the formation of thioester in acetyl coenzyme a synthase

P. W. G. Ariyananda, M. T. Kieber-Emmons, G. P. A. Yap and C. G. Riordan, Dalton Trans., 2009, 4359 DOI: 10.1039/B901192G

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