A pi-basic rhenium center that effects cyclohexene isomerization to a beta-agostic carbene ligand.

abstract

• The molecule (PNPR)Re(H)4 (PNPR = (R2PCH2SiMe2)2N, R = iPr or cyclohexyl) reacts at 20 degrees C with 2 mol of cyclohexene to form equimolar cyclohexane and (PNPR)Re(H)2[=C(CH2)5]. This product is characterized by 1H, 13C, and 31P NMR and by X-ray diffraction as having one CH2 hydrogen (from a carbon located beta to Re) donating to the metal ("agostic CH"). This interaction occurs in preference to PNPR amide nitrogen pi-donation. DFT calculations confirm this agostic interaction, and show that the (PNPR)Re(H)2 fragment indeed reverses the greater stability of free olefin vs free carbene.

authors

• Ozerov, Oleg

published proceedings

• J Am Chem Soc

author list (cited authors)

• Ozerov, O. V., Watson, L. A., Pink, M., & Caulton, K. G.

citation count

• 41

complete list of authors

• Ozerov, Oleg V||Watson, Lori A||Pink, Maren||Caulton, Kenneth G

publication date

• August 2003

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

keywords

• 0306 Physical Chemistry (incl. Structural)

PubMed Central ID

• 12904023

Digital Object Identifier (DOI)

• 10.1021/ja035165x

start page

• 9604

end page

• 9605

volume

• 125

issue

• 32

URL

• http://dx.doi.org/10.1021/ja035165x