%0 Journal Article %A Berclaz, Théo %A Ndiaye, Bassirou %A Bhat, Shrinivasa %A Jouaiti, Abdelaziz %A Geoffroy, Michel %T [M(CO)4PPh3]·- radicals (M = Cr, Mo, W): DFT and single crystal EPR investigations %J Chemical Physics Letters %@ 0009-2614 %V 440 %N 4-6 %P 224-228 %D 2007 %U http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TFN-4NHV4NC-9&_user=779890&_coverDate=06%2F08%2F2007&_rdoc=13&_fmt=summary&_orig=browse&_srch=doc-info(%23toc%235231%232007%23995599995%23656907%23FLA%23display%23Volume)&_cdi=5231&_sort=d&_docanchor=&_ct=42&_acct=C000043220&_version=1&_urlVersion=0&_userid=779890&md5=e5907e50d6ffd1ec10c45caaab962e34 %R 10.1016/j.cplett.2007.04.052 %U http://archive-ouverte.unige.ch/unige:3595 %X [M(CO)4PPh3]•− (M = Mo, W) were trapped at 77 K in X-irradiated single crystals of M(CO)5PPh3 and studied by EPR. Structures of [M(CO)4PPh3]•− (M = Cr, Mo, W) were optimized by DFT; predicted g and 31P-hyperfine tensors agree with experiments for M = Mo, W. The anions adopt a slightly distorted pyramidal structure with PPh3 in basal position and the spin mostly delocalized in a metal-dz2 orbital and carbon-pz orbitals of carbonyls. The EPR tensors are slightly modified by annealing, they suggest that new constraints in the matrix distort the structure of [M(CO)4PPh3]•− (M = Cr, Mo, W).