A CW-EPR, ENDOR and special TRIPLE resonance study of a novel magnesium ketyl radical.
In this paper, the paramagnetic properties of a novel magnesium ketyl radical (compound 1), formed by reduction of benzophenone with a dimeric Mg(I) complex in the presence of dimethylaminopyridine, are described. Using CW EPR, ENDOR and special TRIPLE resonance, the spin distribution in the radical has been explored at variable temperatures (200-298 K). At 298 K, most of the unpaired spin is found to be confined to the (OCPh(2)(•)) fragment based on the hyperfine couplings (hfc's) of o-H = 8.30, m-H = 3.00 and p-H = 9.95 MHz. Smaller hfc's to (25)Mg (5.54 MHz) and (14)N(DMAP) (0.90 MHz) were also evidenced in the 298 K EPR spectrum, indicating some spin delocalisation onto the Mg(Nacnac)(DMAP) fragment. At lower temperatures, restricted rotations of the diphenyl rings create an inequivalent spin distribution in the two rings, with o(1)-H = 8.80, o(2)-H = 7.85, m-H = 3.00 and p-H = 10.00 MHz.
School of Chemistry, Cardiff University, Park Place, Cardiff, UK. murphydm@cardiff.ac.uk
Damien M
DM
Murphy
Lucia E
LE
McDyre
Emma
E
Carter
Andreas
A
Stasch
Cameron
C
Jones
D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry; D008274:Magnesium / Q000737:chemistry*; D008280:Magnetics; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D019163:Reducing Agents / Q000737:chemistry; D013696:Temperature
D005609:Free Radicals; D009942:Organometallic Compounds; D019163:Reducing Agents; D008274:Magnesium