Exposure of MeTHF solutions of M(CO)6 (M=Cr, Mo, W) to γ-rays or photoionization with TMPD at 77 K gives paramagnetic species attributed to 17 electron radical anions M(CO) . The excess energy arising from the primary electron capture process is responsible of the fast M—CO bond breaking which prevents the trapping of 19-electron species M(CO) . Experimental and EHT-MO calculated g-tensors of the pentacoordinated anions are consistent with a square pyramidal C4ν structure having the unpaired electron in a molecular orbital with a high dz2 character.
Matrix isolation and ESR study of unstable intermediate generated by radiation techniques from metal carbonyl complexes
BUTTAFAVA, ARMANDO;FAUCITANO, ANTONIO;MARTINOTTI, FAUSTA
1991-01-01
Abstract
Exposure of MeTHF solutions of M(CO)6 (M=Cr, Mo, W) to γ-rays or photoionization with TMPD at 77 K gives paramagnetic species attributed to 17 electron radical anions M(CO) . The excess energy arising from the primary electron capture process is responsible of the fast M—CO bond breaking which prevents the trapping of 19-electron species M(CO) . Experimental and EHT-MO calculated g-tensors of the pentacoordinated anions are consistent with a square pyramidal C4ν structure having the unpaired electron in a molecular orbital with a high dz2 character.File in questo prodotto:
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