“…Simultaneously in our group, efforts directed toward the syntheses of ruthenium hydride complexes showed that a secondary alcohol could provide an efficient hydrogen source and that molecular hydrogen was not needed and indeed was often an impediment to the isolation of ruthenium hydride complexes − This prompted investigation of the use of a secondary alcohol, sec -butyl alcohol, as the solvent in the dechlorination of chloroarenes in the absence of hydrogen gas (eq 4). …”
The catalytic dechlorination of aryl chlorides performed by RuHCl(H2)2(PCy3)2 and RuH2(H2)2(PCy3)2 in alcohols is rapid and complete within 1 h. The mechanism involves a transfer
hydrogenation step with participation of the alcohol. The system exhibits significant
functional group tolerance. The catalyst can be generated in situ from [RuCl2(COD)]
x
(COD
= cyclooctadiene) and 2 equiv of phosphine (PCy3 or PiPr3). Catalytic conversions are similar
to those observed when an isolated precatalyst is used. Mechanistic considerations and the
scope of the process are discussed.
“…Simultaneously in our group, efforts directed toward the syntheses of ruthenium hydride complexes showed that a secondary alcohol could provide an efficient hydrogen source and that molecular hydrogen was not needed and indeed was often an impediment to the isolation of ruthenium hydride complexes − This prompted investigation of the use of a secondary alcohol, sec -butyl alcohol, as the solvent in the dechlorination of chloroarenes in the absence of hydrogen gas (eq 4). …”
The catalytic dechlorination of aryl chlorides performed by RuHCl(H2)2(PCy3)2 and RuH2(H2)2(PCy3)2 in alcohols is rapid and complete within 1 h. The mechanism involves a transfer
hydrogenation step with participation of the alcohol. The system exhibits significant
functional group tolerance. The catalyst can be generated in situ from [RuCl2(COD)]
x
(COD
= cyclooctadiene) and 2 equiv of phosphine (PCy3 or PiPr3). Catalytic conversions are similar
to those observed when an isolated precatalyst is used. Mechanistic considerations and the
scope of the process are discussed.
“…A preferential selective reduction to saturated ketones is observed for the α,β-unsaturated ketones case. The Tp Me2 -complex 160 also shows good catalytic activity for the reduction of unsaturated ketones by dihydrogen and by hydrogen transfer from alcohols in basic media …”
Section: Rutheniummentioning
confidence: 99%
“…The Tp Me2 -complex 160 also shows good catalytic activity for the reduction of unsaturated ketones by dihydrogen and by hydrogen transfer from alcohols in basic media. 212 2.6.5. Other σ-Bond Activations.…”
The preparation, structure, dynamic behavior in solution, and reactivity of polyhydride complexes of platinum group metals, described during the last three decades, are contextualized from both organometallic and coordination chemistry points of view. These compounds, which contain dihydrogen, elongated dihydrogen, compressed dihydride, and classical dihydride ligands promote the activation of B-H, C-H, Si-H, N-H, O-H, C-C, C-N, and C-F, among other σ-bonds. In this review, it is shown that, unlike other more mature areas, the chemistry of polyhydrides offers new exciting conceptual challenges and at the same time the possibility of interacting with other fields including the conversion and storage of regenerative energy, organic synthetic chemistry, drug design, and material science. This wide range of possible interactions foresees promising advances in the near future.
“…Because excess H 2 is usually present in hydrogenations, the g 2 -H 2 behaves similar to a weakly coordinated solvent molecule and can compete with solvent binding as in scheme 7. Catalysts include both neutral and cationic systems with labile H 2 such as OsHCl(H 2 )(CO)P 2 [45-47], RuH 2 (H 2 )P 3 [48][49][50][51][52][53], RuH 2 (H 2 )P 2 [51,54,55], [MH(H 2 )P 4 ] + (M=Fe, Ru, Os) [35,[56][57][58][59][60][61][62][63][64], [IrH 2 (H 2 )P 3 ] + [65][66][67], and Tp*RuH 2 (H 2 ) [68]. Some patented processes include hydrogenation of nitriles and nitro compounds, e.g.…”
Section: Hydrogenation Catalyzed By H 2 Complexes In a Precursor Rolementioning
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