Experimental and Theoretical Study of CO2 Insertion into Ruthenium Hydride Complexes.

The ruthenium hydride [RuH(CNN)(dppb)] (1; CNN = 2-aminomethyl-6-tolylpyridine, dppb = 1,4-bis(diphenylphosphino)butane) reacts rapidly and irreversibly with CO2 under ambient conditions to yield the corresponding Ru formate complex 2. In contrast, the Ru hydride 1 reacts with acetone reversibly to generate the Ru isopropoxide, with the reaction free energy ΔG°(298 K) = -3.1 kcal/mol measured by (1)H NMR in tetrahydrofuran-d8. Density functional theory (DFT), calibrated to the experimentally measured free energies of ketone insertion, was used to evaluate and compare the mechanism and energetics of insertion of acetone and CO2 into the Ru-hydride bond of 1. The calculated reaction coordinate for acetone insertion involves a stepwise outer-sphere dihydrogen transfer to acetone via hydride transfer from the metal and proton transfer from the N-H group on the CNN ligand. In contrast, the lowest energy pathway calculated for CO2 insertion proceeds by an initial Ru-H hydride transfer to CO2 followed by rotation of the resulting N-H-stabilized formate to a Ru-O-bound formate. DFT calculations were used to evaluate the influence of the ancillary ligands on the thermodynamics of CO2 insertion, revealing that increasing the π acidity of the ligand cis to the hydride ligand and increasing the σ basicity of the ligand trans to it decreases the free energy of CO2 insertion, providing a strategy for the design of metal hydride systems capable of reversible, ergoneutral interconversion of CO2 and formate.

Chemoselective Pd-catalyzed oxidation of polyols: synthetic scope and mechanistic studies.

The regio- and chemoselective oxidation of unprotected vicinal polyols with [(neocuproine)Pd(OAc)]2(OTf)2 (1) (neocuproine = 2,9-dimethyl-1,10-phenanthroline) occurs readily under mild reaction conditions to generate α-hydroxy ketones. The oxidation of vicinal diols is both faster and more selective than the oxidation of primary and secondary alcohols; vicinal 1,2-diols are oxidized selectively to hydroxy ketones, whereas primary alcohols are oxidized in preference to secondary alcohols. Oxidative lactonization of 1,5-diols yields cyclic lactones. Catalyst loadings as low as 0.12 mol % in oxidation reactions on a 10 g scale can be used. The exquisite selectivity of this catalyst system is evident in the chemoselective and stereospecific oxidation of the polyol (S,S)-1,2,3,4-tetrahydroxybutane [(S,S)-threitol] to (S)-erythrulose. Mechanistic, kinetic, and theoretical studies revealed that the rate laws for the oxidation of primary and secondary alcohols differ from those of diols. Density functional theory calculations support the conclusion that ß-hydride elimination to give hydroxy ketones is product-determining for the oxidation of vicinal diols, whereas for primary and secondary alcohols, pre-equilibria favoring primary alkoxides are product-determining. In situ desorption electrospray ionization mass spectrometry (DESI-MS) revealed several key intermediates in the proposed catalytic cycle.

Nickel dithiolene chelate rings in a new role as eta5-coordinating ligands: synthesis, structural characterization, and redox reactivity of an "Fe2Ni" bis-double-decker.

A bis-double-decker complex has been assembled from the nickel bisdithiolene complex [Ni(S 2C 2Me 2) 2] (1-/2-) and two [Cp*Fe] (+) units (Cp* = C 5Me 5). The complex, [(eta (5)-Cp*-Fe-mu-eta (5),eta (5)-((S 2C 2Me 2) 2Ni)Fe-eta (5)-Cp*] ( n ) ( 1 ( n )), was isolated in two charge states ( n = 0, 1). The structure of 1 (+) was confirmed by X-ray crystallography for 1 (+)PF 6 (-) and 1 (+)BF 4 (-), and it shows the nickel bisdithiolene units pi-donating to iron centers. Both salts crystallize in a centrosymmetric space group (center of inversion at nickel). Computational (density functional theory) data indicate a highly delocalized spin density for 1 (+). The reaction of 1 with 1 or 2 equiv of HBF 4 leads to oxidation to form 1 (+) or 1 (2+), respectively. On an electrochemical time scale, reversibility is observed for the redox series 1/ 1 (+)/ 1 (2+), with an additional slower step for oxidation of 1 (2+).

Amidine-Mediated Zwitterionic Polymerization of Lactide.

The ring-opening polymerization (ROP) of lactide with DBU (1,8-diazabicyclo[5.4.0] undec-7-ene) is described. Room temperature polymerization using the neutral amine catalyst DBU in the absence of any other initiator produces polymers with narrow polydispersities and shows a linear relationship between molecular weight and conversion. The resulting polymers were characterized and determined to be cyclic. DFT calculations support a mechanistic hypothesis involving a zwitterionic acyl amidinium intermediate.

Characterization of a rhodium-sparteine complex, [((-)-sparteine)Rh(eta4-COD)]+: crystal structure and DNMR/DFT studies on ligand-rotation dynamics.

A cationic rhodium-sparteine complex, [((-)-sparteine)Rh(eta(4)-COD)](+) (1(+); COD = 1,5-cyclooctadiene) was obtained, isolated as its tetrafluoroborate salt (1BF(4)), and characterized using X-ray crystallography and multinuclear ((1)H, (13)C) NMR spectroscopy. This is the first structurally characterized sparteine complex of rhodium. The Rh-N bonds are unusually long (2.214(3) and 2.242(3) A), apparently due to steric repulsion between COD and sparteine. (1)H NMR exchange experiments (EXSY) demonstrate a dynamic process that results in an overall 180 degrees rotation of the COD methine protons in solution (CD(2)Cl(2)) with a first-order rate constant of 460 s(-1) at the coalescence temperature (314 K) and interpolated rate constant of 150 s(-1) at 298 K. Temperature-dependent NMR studies yield DeltaH(++) = 13.0 +/- 0.3 kcal mol(-1), DeltaS(++) = -5 +/- 1 cal mol(-1) K(-1), such that DeltaG(298)(++) = 14.3 +/- 0.3 kcal mol(-1). DFT studies (B3LYP) indicate that the loosely bound (-)-sparteine ligand rotates through a pseudo-tetrahedral transition state where both ligands are rotated approximately 90 degrees relative to each other. While both ligands remain bound (eta(4)-COD, kappa(2)-sparteine), bonding to sparteine is weakened much more than bonding to COD in the transition state. DFT computed DeltaG(298)(++) and DeltaS(++) values (15.55 kcal mol(-1) and -2.67 cal mol(-1) K(-1), respectively) agree very well with the experimental values. Attempts to find alternative mechanisms involving partial dechelation of COD and (-)-sparteine yielded slightly higher barriers along with positive DeltaS values for intermediate formation.