TY - JOUR AU - Berclaz, Théo AU - Ndiaye, Bassirou AU - Bhat, Shrinivasa AU - Jouaiti, Abdelaziz AU - Geoffroy, Michel TI - [M(CO)4PPh3]·- radicals (M = Cr, Mo, W): DFT and single crystal EPR investigations PY - 2007 JF - Chemical Physics Letters JA - Chem. Phys. Lett. SN - 0009-2614 VL - 440 IS - 4-6 SP - 224 EP - 228 L1 - http://www.sciencedirect.com/science?_ob=MImg&_imagekey=B6TFN-4NHV4NC-9-K&_cdi=5231&_user=779890&_orig=browse&_coverDate=06%2F08%2F2007&_sk=995599995&view=c&wchp=dGLbVlb-zSkWA&md5=5fd329e3328bd4ac2da2f971b530b5fc&ie=/sdarticle.pdf L2 - http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TFN-4NHV4NC-9&_user=779890&_coverDate=06%2F08%2F2007&_rdoc=13&_fmt=full&_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=58c0f518014fe5bdea4c295e545d555f L3 - 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 L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref00880.png M3 - 10.1016/j.cplett.2007.04.052 UR - http://dx.doi.org/10.1016/j.cplett.2007.04.052 N2 - [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). ID - 880 ER -