Intermediates for methyl carbon-hydrogen activation in binuclear dimethylfulvene ruthenium carbonyl complexes

Abstract

The methyl C-H bonds in the dimethylfulvene complex [ 5 , 1-C 5 H 4 C(CH 3) 2 ]-[Ru(CO) 2 ][Ru(CO) 4 ] are known experimentally to be activated by the central Ru 2 unit to give the dehydrogenation product [ 5 , 3-C 5 H 4 C(CH 2) 2 ][Ru(CO) 2 ][Ru(CO) 3 ]. The mechanistic aspects of this process are explored by a theoretical investigation of the two series of complexes [C 5 H 4 C(CH 3) 2 ]Ru 2 (CO) n and [C 5 H 4 C(CH 2) 2 ]Ru 2 (CO) n (n = 6, 5, 4). Potential reaction intermediates with agostic hydrogen atoms as well as ruthenium carbonyl hydrides and dihydrogen complexes are found.

Hydrogenation of Diisopropylimine over Mesoporous Carbon Supported Metal Catalysts

“…It is well-known that Ni and Ru form carbonyl compounds with CO such as Ni­(CO) 4 , Ru­(CO) 5 , and Ru 3 (CO) 12 , − while Pd and CO hardly form stable carbonyl compounds. Instead, large ligands are usually required to form complexes with Pd to increase their structural stability. , It is also well-known that porous carbons contain large amounts of surface functional groups such as −COOH, whose carbonyl groups might interact with Ni and Ru, affecting their surface chemical properties.…”