Preparation and reactivity of a Ru(0) phosphino-carbene complex.

The reaction of the phosphino-carbene MeNC3H2NPtBu2 with RuHCl(CO)(PPh3)3 is shown to give facile access to the Ru(0) species (MeNC3H2NPtBu2)Ru(CO)(PPh3)2 (). This species undergoes oxidative addition of H2 and silanes to give (MeNC3H2NPtBu2)RuH2(CO)(PPh3)2, (MeNC3H2NPtBu2)Ru H(SiRPh2)(CO)(PPh3) (R = Ph 5, H 6) and (MeNC3H2NPtBu2) RuH(PhSi(SCH2CH2)2O)(CO)(PPh3) .

Phosphine catalyzed reduction of CO2 with boranes.

Phosphine is shown to catalyse the reaction of CO2 with 9-BBN to give mixtures of HCO2(B(C8H14)) 3, H2C(OB(C8H14))24 and MeOB(C8H14) 5; at 0.02 mol% of tBu3P 5 is obtained in 98% yield at 60 °C with TON of almost 5500 and a TOF of 170. Under stoichiometric conditions the species (R3PCH2O)(HC(O)O)B(C8H14) (R = tBu 1,4-MeC6H42) were isolated and characterized.

Carbene-9-BBN ring expansions as a route to intramolecular frustrated Lewis pairs for CO2 reduction.

Reactions of phosphine-derived carbenes with 9-borabicyclo[3.3.1]nonane (9-BBN) result in ring-expansion reactions to generate novel intramolecular frustrated Lewis pairs (FLPs). These FLPs effect the catalytic reduction of CO2 in the presence of boranes to give BOB and methoxy-borate species.

Platinum(II)-catalyzed cross-coupling of polyfluoroaryl imines.

The introduction of fluorine into an organic molecule imparts unique physicochemical properties. Not surprisingly, fluorine is increasingly incorporated into new drugs and agrochemicals. However, aryl fluoride building blocks are only available through synthesis. The ability to cross-couple polyfluoroaromatics selectively could provide a convenient route to functionalized fluoroaromatics. We report herein the first examples of Pt-catalyzed cross-coupling of aryl fluorides. The methylated products can potentially serve as precursors to a wide range of functionalized fluorinated small molecules.