TY - JOUR
T1 - Synthesis and isomerisation of two metallated N,O-complexes of ruthenium
T2 - Models for the Murai reaction
AU - Jazzar, Rodolphe F.R.
AU - Varrone, Maurizio
AU - Burrows, Andrew D.
AU - MacGregor, Stuart A.
AU - Mahon, Mary F.
AU - Whittlesey, Michael K.
PY - 2006/2/1
Y1 - 2006/2/1
N2 - Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh 3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (ΔH‡ = 195 ± 41 kJ mol-1; ΔS‡ = 232 ± 62 J mol -1 K-1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2′-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.
AB - Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh 3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (ΔH‡ = 195 ± 41 kJ mol-1; ΔS‡ = 232 ± 62 J mol -1 K-1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2′-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.
KW - Cyclometallation
KW - Density functional theory
KW - Hydride ligands
KW - Murai reaction
KW - Phosphine ligands
KW - Ruthenium complexes
UR - http://www.scopus.com/inward/record.url?scp=30944467923&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2005.05.021
DO - 10.1016/j.ica.2005.05.021
M3 - Article
AN - SCOPUS:30944467923
SN - 0020-1693
VL - 359
SP - 815
EP - 820
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 3
ER -