Rhenium dinitrogen complex (eta-C/sub 5/Me/sub 5/)Re(CO)(PMe/sub 3/)(N/sub 2/). Facile photochemical generation of a rhenium intermediate and oxidative addition of hydrocarbon C-H bonds

Journal Article · Wed May 28 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00271a052· OSTI ID:5454904

Klahn-Oliva, A H; Singer, R D; Sutton, D

As part of our continuing investigation of dinitrogen, diazenide, hydrazide, and related ligands, we have synthesized the trimethylphosphine-substituted (pentamethylcyclopentadienyl)rhenium dinitrogen complex Cp*Re(CO)(PMe/sub 3/)(N/sub 2/)(1) (Cp* = eta-C/sub 5/Me/sub 5/). The MeCN complex (Cp*Re(CO)(MeCN)(p-N/sub 2/C/sub 6/H/sub 4/OMe)(BF/sub 4/) (2) was treated with PMe/sub 3/ to give (Cp*Re(CO)(PMe/sub 3/)(p-N/sub 2/C/sub 6/H/sub 4/OMe)(BF/sub 4/) (3), which was converted to 1 by using t-BuLi. Complex 1 is a pale yellow solid that is stable indefinitely if air is excluded and is inert to thermal exchange of the N/sub 2/ ligand in N/sub 2/-saturated organic solvents at ambient temperature as judged from the IR and /sup 15/N NMR spectra of 96% /sup 15/N/sub ..cap alpha../-enriched samples. Nevertheless, 1 undergoes photochemical reactions in which the N/sub 2/ ligand is readily displaced. Most interesting and topical, in view of the current interest in C-H activation by soluble transition-metal complexes, is the concurrent formation of a rhenium intermediate capable of insertion into selected hydrocarbon C-H bonds in high yield to give isolable derivatives.

• Research Organization: Simon Fraser Univ., Burnaby, British Columbia
• OSTI ID: 5454904
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:11; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
CARBONYLS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
LIGANDS
MAGNETIC RESONANCE
NITROGEN COMPLEXES
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
RESONANCE
RHENIUM COMPLEXES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES