FLP catalysis: main group hydrogenations of organic unsaturated substrates.

This article is focused on recent developments in main group mediated hydrogenation chemistry and catalysis using "frustrated Lewis pairs" (FLPs). The broading range of substrates and catalyst systems is reviewed and the advances in catalytic reductions and the development of stereoselective, asymmetric reductions made since 2012 is considered.

The air-stable carbocation salt [(MeOC6H4)CPh2][BF4] in Lewis acid catalyzed hydrothiolation of alkenes.

Markovnikov hydrothiolation of 1,1-disubstituted and trisubstituted olefins (20 examples) is catalyzed by Lewis acids, including the air-stable trityl-cation salt [(MeOC6H4)CPh2][BF4] 3.

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) .