NONPARAMETERIZED MO CALCULATIONS OF LIGAND-BRIDGED M2 (CO)8 - (MU2 -X)2- TYPE DIMERS CONTAINING METAL-METAL INTERACTIONS - EVIDENCE FOR DICTATION OF STEREOCHEMISTRY BY ONE-ELECTRON AND 2-ELECTRON METAL-METAL SIGMA-TYPE BONDS
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abstract
Nonparameterized MO calculations performed on the (edge-bridged)-bioctahedral metal dimers of the Dessy-characterized [Cr2(CO)8(2-PR2) 2](n-2) series and of the [Mn2(CO)8(2-PR2) 2]n series (n = 0, +1, +2) have revealed that the corresponding dimeric pairs with n = 0, +1, and +2 have two, one, and no electrons, respectively, in the antibonding 2b3u MO corresponding to a "net" no-electron metalmetal bond, a "net" one-electron metalmetal bond, and a two electron metalmetal bond. Of prime significance is that this 2b3u MO, which is the LUMO in both electron-pair (metalmetal)-bonded dimers (n = +2) and the HOMO in the corresponding dimers to which one or two electrons have been added, is found to be largely composed of in-plane antibonding {black star}-type dimetal orbital character rather than either out-of-plane {black star}-type dimetal antibonding orbital character or bridging-ligand orbital character. These MO results are also shown to be completely compatible with the available spectral and X-ray data. 1974.
