Secondary Oxide Phosphines to Promote Tandem Acyl-Alkyl Coupling/Hydrogen Transfer to Afford (Hydroxyalkyl)rhodium Complexes. Theoretical and Experimental Studies.

Acyl(?-norbornenyl)rhodium(III) dimer [Rh(?-Cl)(CHNCO)(CH)L] (1) (CH = ?-norbornenyl; L = 4-picoline, isoquinoline) reacts with diphenylphosphine oxide (SPO) to undergo a one-pot reaction involving (i) cleavage of the chloride bridges and coordination of the phosphine, (ii) C-C bond coupling between acyl and norbornenyl in a 18e species, and (iii) ligand-assisted outer-sphere O(P)-to-O(C) hydrogen transfer, to afford mononuclear 16e species [RhCl{(CHNC(O)CH)(PhPO)H}(L)] (2) containing a quinolinyl-(norbornenylhydroxyalkyl) fragment hydrogen-bonded to a ?- P-phosphinite ligand. Pentacoordinated 2, which adopt a distorted trigonal bipyramidal structure, are kinetic reaction products that transform into the thermodynamic favored isomers 3. Structures 3 contain an unusual weak ?-C anagostic interaction involving the rhodium atom and one carbon atom of the olefinic C-H bond of the norbornenyl substituent in the chelating quinolinyl-hydroxyalkyl moiety. Their structure can be described as pseudoctahedral, through a 5 + 1 coordination, with the anagostic interaction in a trans disposition with respect to the phosphorus atom of the phosphinite ligand. Complexes were characterized in solution by NMR spectroscopy and electrospray ionization mass spectrometry. Complex [RhCl{(CHNC(O)CH)(PhPO)H}(4-picoline)] (3a) was also identified by X-ray diffraction. Density functional theory calculations confirm the proposed structures by a plausible set of mechanisms that accounts for the 1 (monomer) ? 2 ? 3 transformation. Lowest-energy pathways involve reductive elimination of quinolinylnorbornenylketone, still coordinated in the rhodium(I) species thus formed, followed by O-to-O hydrogen transfer from ?- P-SPO to the sp hybridized carbonyl group (formal alkoxide) avoiding the otherwise expected classical release of ketone. Theoretical C NMR studies also confirm the experimental spectral data for the considered structures.