Metal-metal bonds involving the f elements. 4. Molecular orbital studies of metal-metal and metal-ligand interactions in dinuclear uranium(V) systems

1991 ◽  
Vol 30 (10) ◽  
pp. 2265-2272 ◽  
Author(s):  
Roger H. Cayton ◽  
Kevin J. Novo-Gradac ◽  
Bruce E. Bursten

Logical methods for preparing small metal clusters with heteronuclear metal-metal bonds can be devised by appreciating the isolobal relationships that exist between certain metal ligand combinations and organic fragments. Thus the group W(CO) 2 (r|-C 5 H 5 ) has frontier orbitals of similar pattern to those of CH, while those of Rh(CO) (r|-C 5 Me 5 ) and CH 2 are also similar. This paper shows how such ideas have been employed to generate compounds with bonds between rhodium and other metals.


1994 ◽  
Vol 72 (10) ◽  
pp. 2176-2182 ◽  
Author(s):  
Pierre D. Harvey ◽  
Peter Johnston ◽  
Neil J. Coville

The properties of the heteronuclear metal–metal bonds in the unbridged [η5–C5H5)Fe(CO)2Re(CO)5−n(CNR)n] and [(η5–C9H7)Fe(CO)2Re(CO)5−n(CNR)n complexes (n = 0, 1, 2; R = tert-butyl (tBu) and 2,6-dimethylphenyl (Xy)) and the two equatorially substituted isomers of [MnRe(CO)8(CN-tBu)2] have been investigated theoretically by Extended Hückel Molecular Orbital calculations (EHMO) and experimentally by UV–visible spectroscopy, electrochemistry, and by microRaman or FT-Raman spectroscopy. The expected dσ* orbital is the lowest unoccupied molecular orbital (LUMO), mainly fabricated by interactions of the metal [Formula: see text] orbital, but the dπ* and dσ orbitals are the highest occupied molecular orbital (HOMO) and HOMO-1, respectively, as demonstrated experimentally from the UV–visible spectra. The EHMO computations demonstrate the mixing between these two dπ* (and dδ) and dσ MO orbitals. The influence of substituent effects on the spectroscopic and electrochemical properties is complicated and is interpreted in terms of inductive effects and relative destabilisation of the dσ, dπ*, and dσ* molecular orbitals. Finally, the metal–metal stretching frequencies for four mixed metal dimers (MnRe and FeRe) are reported.


2000 ◽  
Vol 19 (24) ◽  
pp. 5049-5062 ◽  
Author(s):  
Faming Jiang ◽  
Hilary A. Jenkins ◽  
Kumar Biradha ◽  
Harry B. Davis ◽  
Roland K. Pomeroy ◽  
...  

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