Rhodium complexes electronic structure

Ligand 73 was prepared directly from a single enantiomer of the corresponding naphthol of QUINAP 60, an early intermediate in the original synthesis, and both enantiomers of BINOL. Application in hydroboration found that, in practice, only one of the cationic rhodium complexes of the diastereomeric pair proved effective, (aA, A)-73. While (aA, A)-73 gave 68% ee for the hydroboration of styrene (70% yield), the diastereomer (aA, R)-73 afforded the product alcohol after oxidation with an attenuated 2% ee (55% yield) and the same trend was apparent in the hydroboration of electron-poor vinylarenes. Indeed, even with (aA, A)-73, the asymmetries induced were very modest (31-51% ee). The hydroboration pre-catalyst was examined in the presence of catecholborane 1 at low temperatures and binuclear reactive intermediates were identified. However, when similar experiments were conducted with QUINAP 60, no intermediates of the same structural type were found.100... 

Scheme 6.27 considers other, formally confined, conformers of cycloocta-l,3,5,7-tetraene (COT) in complexes with metals. In the following text, M(l,5-COT) and M(l,3-COT) stand for the tube and chair structures, respectively. M(l,5-COT) is favored in neutral (18-electron) complexes with nickel, palladium, cobalt, or rhodium. One-electron reduction transforms these complexes into 19-electron forms, which we can identify as anion-radicals of metallocomplexes. Notably, the anion-radicals of the nickel and palladium complexes retain their M(l,5-COT) geometry in both the 18- and 19-electron forms. When the metal is cobalt or rhodium, transition in the 19-electron form causes quick conversion of M(l,5-COT) into M(l,3-COT) form (Shaw et al. 2004, reference therein). This difference should be connected with the manner of spin-charge distribution. The nickel and palladium complexes are essentially metal-based anion-radicals. In contrast, the SOMO is highly delocalized in the anion-radicals of cobalt and rhodium complexes, with at least half of the orbital residing in the COT ring. For this reason, cyclooctateraene flattens for a while and then acquires the conformation that is more favorable for the spatial structure of the whole complex, namely, M(l,3-COT) (see Schemes 6.1 and 6.27). 

Even though the outlined approach allowed the successful rationalisation of many experimentally observed shift/structure and shift/reactivity correlations, Leitner et al. have pointed out that such relations cannot be expected to be universally valid and require that structural variations are modest and avoid large simultaneous changes in parameters that may have opposite effects on metal chemical shifts.61 To overcome these drawbacks and establish a more rational interpretation of chemical shift trends, they used a combination of experimental and computational efforts to assess the importance of different electronic and structural factors on the metal chemical shifts of a series of rhodium complexes with bidentate chelating bisphosphine ligands. The basis of their approach is first the validation of experimentally observed metal shifts by... 

The complexes in Table I have been assigned an end-on geometry on the basis of spectroscopic data, chemical behavior, and, in the case of a macrocyclic rhodium complex, X-ray crystallographic data (53). The 0-0 stretching frequencies and 0-0 bond lengths are useful indicators of the electronic structure of coordinated dioxygen (54-59),... 

Steric effects in the alkene structure also affect linearity. As a result, quaternary carbon atoms are rarely formed in hydroformylation45 In contrast, electronic effects in hydroformylation of arylalkenes often result in the predominant formation of the branched aldehyde.6 40 43 46- 8 Styrene has a marked tendency to form 2-phenylpropanal when hydroformylated in the presence of rhodium catalysts. Rhodium complexes modified by biphosphine49 or mixed amino phosphine oxide ligands50 were shown to give the branched aldehyde with high reactivity and selectivity (iso normal ratios <61.5). 

The structurally analogous rhodium complex Rh2( i-ap)4 2( i-C= CC=C) (175, M = Rh, LL = ap) was obtained stepwise from Rh2( i-ap)4Cl with LiC=CSiMe3, desilylation with LiBu and further reaction with Rh2( i-ap)4Cl.323 However, in this case UV spectroscopy indicates little electronic communication between the two Rh2 centers. 

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