Abstract
Extended Huckel molecular orbital calculations give a positive Mulliken overlap population between cis non bonded dihydride and trihydrides in transition-metal complexes (i.e., cis-(H) 2 Os(CO) 4 and CpIr(PH 3 )(H) 3 + ). In contrast, isolobal organic systems (CH 4 and D 3h CH 5 + , respectively) show no tendency for such a positive long-range interaction. The results are interpreted in terms of variable electron transfer from the symmetry-adapted polyhydride H n molecular orbitals into those of the metal or organic fragment
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