A versatile rigid binucleating ligand for Rh2(μ-Cl)2 moieties: its application as a catalyst in hydrogenation and cyclopropanation

A rigid non-deforming "MCl 2 M" binucleating ligand [7,8-μ-S(4'-C 6 H 3 (CH 3 ))S-C 2 B 9 H 1 0 ] - able to held the two rhodium atoms in a cooperative distance has been synthesized. The original two bridging chlorides are retained in [Rh 2 (C 5 Me 5 ) 2 Cl 2 {7,8-μ-S(4'-C 6 H 3 (CH 3 ))S-C 2 B 9 H 1 0 }] + . Hydrogenation of 1-hexene is 10 times faster with [Rh 2 (C 5 Me 5 ) 2 Cl 2 {7,8-μ-S(4'-C 6 H 3 (CH 3 ))S-C 2 B 9 H 1 0 }] + than with [Rh 2 (C 5 Me 5 ) 2 Cl 4 ]. A hydrogenation mechanism has been proposed which assumes that [Rh 2 (C 5 Me 5 ) 2 (Cl)(H){7,8-μ-S(4'-C 6 H 3 (CH 3 ))S-C 2 B 9 H 1 0 }] + is the first generated species in the process.

Assessment of Catalysis by Arene‐Ruthenium Complexes Containing Phosphane or NHC Groups bearing Pendant Conjugated Diene Systems

Two p-cymene-ruthenium complexes 1 and 2 were isolated in high yields by treating the [RuCl2(p-cymene)]2 dimer with new hybrid phosphane- or NHC-linked diene ligands. Both complexes were fully characterized by NMR spectroscopy, and the molecular structure of the ruthenium–p-cymene complex 1, containing the phosphane–diene ligand system, was determined by X-ray diffraction analysis. The catalytic activities of both compounds were probed in atom-transfer radical addition (ATRA) and polymerization (ATRP), in the cyclopropanation of olefins, in the ring-opening metathesis polymerization (ROMP) of norbornene, and in the synthesis of enol esters from hex-1-yne and 4-acetoxybenzoic acid.

ATRP of methyl methacrylate catalysed by novel homo- and heterobimetallic ruthenium complexes

ATRP of Methacrylates Catalysed by Homo- and Heterobimetallic Ruthenium Complexes

The catalytic activity of a series of ruthenium-based homo-and heterobimetallic complexes was determined by investigating the atom transfer radical polymerisation of methyl methacrylate. The complexes under investigation were [(arene)Ru(μ-Cl) 3 RuCl(C 2 H 4 )-(L)] (L = PCy 3 or a N-heterocyclic carbene ligand), [(p-cymene )-Ru(/l-Cl) 3 RuCl(=C=CHR)(PCy 3 )] (R = Ph or t-Bu), and [RuCl 2 -(p-cymene) {PCy 2 (CH2) 2 (n 5 -C 5 H 4 )TiX 2 (n 5 -C 5 H 5 )}] (X = Cl, F, and OBz). The catalytic activity of a variety of related [(p-cymene)-ClRu(μ-Cl) 2 Ru(O/\N)(=CHPh)] complexes (O^N is a Schiff base ligand) is also reported. The results clearly demonstrate that the ligands strongly affect the abili…

CCDC 1056295: Experimental Crystal Structure Determination

Related Article: Johann Baraut, Alexandre Massard, Florian Chotard, Ewen Bodio, Michel Picquet, Philippe Richard, Yannick Borguet, François Nicks, Albert Demonceau, Pierre Le Gendre|2015|Eur.J.Inorg.Chem.||2671|doi:10.1002/ejic.201500054

CCDC 1023384: Experimental Crystal Structure Determination

Related Article: Johann Baraut, Alexandre Massard, Florian Chotard, Ewen Bodio, Michel Picquet, Philippe Richard, Yannick Borguet, François Nicks, Albert Demonceau, Pierre Le Gendre|2015|Eur.J.Inorg.Chem.||2671|doi:10.1002/ejic.201500054