Michael Montag

Aldehyde binding through reversible C-C coupling with the pincer ligand upon alcohol dehydrogenation by a PNP-ruthenium catalyst

Primary alcohol dehydrogenation by a PNP-Ru(II) catalyst was probed by low-temperature NMR experiments. Facile dehydrogenation occurred at -30 °C, but the resulting aldehydes were not found in solution, as they were trapped by the catalyst through a new mode of metal-ligand cooperation involving Ru-O coordination and an unusual, highly reversible C-C coupling with the PNP pincer ligand.

Effect of CO on the oxidative addition of arene C-H bonds by cationic rhodium complexes.

Sequential addition of CO molecules to cationic aryl-hydrido Rh(III) complexes of phosphine-based (PCP) pincer ligands was found to lead first to C-H reductive elimination and then to C-H oxidative addition, thereby demonstrating a dual role of CO. DFT calculations indicate that the oxidative addition reaction is directly promoted by CO, in contrast to the commonly accepted view that CO hinders such reactions. This intriguing effect was traced to repulsive pi interactions along the aryl-Rh-CO axis, which are augmented by the initially added CO ligand (due to antibonding interactions between occupied Rh d(pi) orbitals and occupied pi orbitals of both CO and the arene moiety), but counteracted by the second CO ligand (due to significant pi back-donation). These repulsive interactions were themselves linked to significant weakening of the pi-acceptor character of CO in the positively charged rhodium complexes, which is concurrent with an enhanced sigma-donating capability. Replacement of the phosphine ligands by an analogous phosphinite-based (POCOP) pincer ligand led to significant changes in reactivity, whereby addition of CO did not result in C-H reductive elimination, but yielded relatively stable mono- and dicarbonyl aryl-hydrido POCOP-Rh(III) complexes. DFT calculations showed that the stability of these complexes arises from the higher electrophilicity of the POCOP ligand, relative to PCP, which leads to partial reduction of the excessive pi-electron density along the aryl-Rh-CO axis. Finally, comparison between the effects of CO and acetonitrile on C-H oxidative addition revealed that they exhibit similar reactivity, despite their markedly different electronic properties. However, DFT calculations indicate that the two ligands operate by different mechanisms.

The Impact of Weak C-H···Rh Interactions on the Structure and Reactivity of trans-[Rh(CO)2(phosphine)2]+ : An Experimental and Theoretical Examination

The crystal structure of the new cationic Rh(I) complex trans-[Rh(CO)(2)(L)(2)]BF(4) (L=alpha(2)-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H...Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar Rh(I) complex, in which these C-H...Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.

syn-Bimane as a chelating O-donor ligand for palladium(II)

A cationic Pd(ii) complex containing syn-(Me,Me)bimane as a ligand was prepared and fully characterized. This complex represents the first well-defined case of a bimane scaffold coordinated to a metal center. The strongly-fluorescent syn-bimane chelates the Pd(ii) center via its carbonyl oxygen atoms, affording a non-fluorescent complex. The crystal structure of this complex shows that the coordinated bimane departs from planarity, with its bicyclic framework bent about the N-N bond. Spectroscopic evidence demonstrates that bimane coordination is reversible in solution.

Quenching of syn-bimane fluorescence by Na+ complexation

The fluorescent dye syn-(Me,Me)bimane interacts with the biorelevant Na+ ion to form labile complexes, three of which were crystallographically characterized, exhibiting new modes of bimane coordination. In water, as well as in organic solvents, Na+ complexation induces the quenching of bimane fluorescence.