In the presence of 2-phosphino-substituted imidazole ligands and Ru3(CO)12 or Ru(methylallyl)2(COD) direct hydroformylation and hydrogenation of alkenes to alcohols takes place. In addition to terminal alkenes, also more challenging internal olefins are converted preferentially to industrially important linear alcohols in high yield (up to 88%) and regioselectivity (n:iso up to 99:1).

The ruthenium-catalyzed hydroformylation of 1- and 2-octene to give preferentially the corresponding linear aldehyde is reported. The catalyst system comprising of Ru3 (CO)12 and an imidazole-substituted monophosphine ligand allows for high chemo- and regioselectivity. The hydroformylation proceeds with unprecedented rates for a ruthenium-based catalyst.

An alternative ruthenium-based catalyst for the hydroesterification of olefins with formates is reported. The good activity of our system is ensured by the use of a bidentate P,N-ligand and ruthenium dodecacarbonyl. A range of formates can be used for selective alkoxycarbonylation of aromatic olefins. In addition, the synthesis of selected aliphatic esters is realized. The proposed active ruthenium complex has been isolated and characterized.

Homogeneous ruthenium complexes modified by imidazole-substituted monophosphines as catalysts for various highly efficient hydroformylation reactions were characterized by in situ IR spectroscopy under reaction conditions and NMR spectroscopy. A proper protocol for the preformation reaction from [Ru3 (CO)12] is decisive to prevent the formation of inactive ligand-modified polynuclear complexes. During catalysis, ligand-modified mononuclear ruthenium(0) carbonyls were detected as resting states. Changes in the ligand structure have a crucial impact on the coordination behavior of the ligand and consequently on the catalytic performance. The substitution of CO by a nitrogen atom of the imidazolyl moiety in the ligand is not a general feature, but it takes place when structural prerequisites of the ligand are fulfilled.

The title reaction gives preferentially the linear aldehyde.

Ruthenium-Catalyzed Hydroformylation/Reduction of Olefins to Alcohols: Extending the Scope to Internal Alkenes. -(WU, L.; FLEISCHER, I.; JACKSTELL, R.; PROFIR, I.; FRANKE, R.; BELLER*, M.; J. Am. Chem. Soc. 135 (2013) 38, 14306-14312, http://dx.