Published in Organometallics
The synthesis, characterization, and catalytic activity of low-spin {CoNO}8 pincer complexes of the type [Co(PCP)(NO)(H)] are described. These compounds are obtained either by reacting [Co(PCP)(κ2-BH4)] with NO and Et3N or, alternatively, by reacting [Co(PCP)(NO)]+ with boranes, such as NH3·BH3 in solution. The five-coordinate, diamagnetic Co(III) ...
Published in Organometallics
We report a variety of manganese-based catalysts containing both chelating diphosphine (bis(diphenylphosphino)methane (dppm: 1 , 2 , and 7 ) or 1,2-bis(diphenylphosphino)ethane (dppe: 3 )), and mixed-donor phosphinoamine (2-(diphenylphosphino)ethylamine (dppea: 4 – 6 )) ligands for the upgrading of ethanol and methanol to the advanced biofuel isobu...
Published in Organometallics
The use of the bis(1-piperidinyl)-substituted carbodiphosphorane (Ph2(Pip)P)2C ( 1 ) as an NCN ligand for the stabilization of phosphorus cations was studied. A simple ligand for halide exchange allowed the synthesis and isolation of a series of phosphorus monocations of the type [ 1 -PR2]+ (with R = Cl, Br, I, CyCl, Ph). These cations exhibit char...
Published in Organometallics
The reaction of coordinatively unsaturated Co(II) PCP pincer complexes with nitric oxide leads to the formation of new, air-stable, diamagnetic mono nitrosyl compounds. The synthesis and characterization of five- and four-coordinate Co(III) and Co(I) nitrosyl pincer complexes based on three different ligand scaffolds is described. Passing NO throug...
Published in Organometallics
In this contribution a convenient synthetic method to obtain the previously unknown dianionic cyclic silenolates and germenolates is described. These dianions 2a , b and 4a , b are easily accessible via a one-pot synthetic protocol in high yields. Their structural properties were analyzed by a combination of NMR, single-crystal X-ray crystallograph...
Published in Organometallics
Introducing transition metals into frustrated Lewis pair systems has attracted considerable attention in recent years. Here we report a selection of three metal-only frustrated systems based on Au(I)/Pt(0) combinations and their reactivity toward alkynes. We have inspected the activation of acetylene and phenylacetylene. The gold(I) fragments are s...
Published in Organometallics
Published in Organometallics
Titanium(IV) complexes of amino-tris(phenolate) ligands (LTiX, X = chloride, isopropoxide) together with bis(triphenylphosphine)iminium chloride (PPNCl) are active catalyst systems for the ring-opening copolymerization of carbon dioxide and cyclohexene oxide. They show moderate activity, with turnover frequency values of ∼60 h-1 (0.02 mol % of cata...
Published in Organometallics
Sila-Peterson type reactions of the 1,4,4-tris(trimethylsilyl)-1-metallooctamethylcyclohexasilanes (Me3Si)2Si6Me8(SiMe3)M ( 2a , M = Li; 2b , M = K) with various ketones were investigated. The obtained products strongly depend on the nature of the ketone component. With 2-adamantanone 2a,b afforded the moderately stable silene 3 . 3 is the first ex...
Published in Organometallics
A method for the resolution of η 2-alkene-complex isomers of the type MoTp(NO)(DMAP)( η 2-alkene) and WTp(NO)(PMe3)( η 2-alkene) (where Tp = hydridotris(pyrazolyl)-borate and DMAP = 4-(dimethylamino)pyridine) has been explored. Alkene and polyene compounds form as a mixture of kinetically trapped isomers. For both types of complexes, it was found t...
