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 00:00:00 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), Vol. 108:11
• Country of Publication: United States
• Language: English

Related Subjects

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