Acyl(sigma-norbornenyl)rhodium(III) dimer [Rh(y-Cl)(C9H6NCO)(C7H9)L](2) (1) (C7H9 = sigma-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 [Rhaf (C9H6NC (0)C7H9) (Ph2PO)H} (L)] (2) containing a quinolinyl-(norbornenylhydroxyalkyl) fragment hydrogen-bonded to a kappa(l)-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 eta(1)-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 S + 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 [RhC11(C9H6NC(O)C7H9)(Ph2PO)H}(4-picoline)1 (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 0-to-0 hydrogen transfer from K1-P-SPO to the spa hybridized carbonyl group (formal alkoxide) avoiding the otherwise expected classical release of ketone. Theoretical '3C NMR studies also confirm the experimental spectral data for the considered structures.