TY - JOUR
T1 - Synthesis of [Ru(CO)2(PPh3)(SP)] and [Ru(CO)(PPh3)2(SP)] and their catalytic activities for the hydroamination of phenylacetylene
AU - Mizushima, Eiichiro
AU - Chatani, Naoto
AU - Kakiuchi, Fumitoshi
N1 - Funding Information:
This work was supported, in part, by PRESTO, JST. We thank the Instrumental Analysis Center, Faculty of Engineering, Osaka University for assistance in obtaining NMR and FAB mass spectroscopy.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 2006/12/15
Y1 - 2006/12/15
N2 - The reaction of [Ru(CO)2(PPh3)3] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)2(PPh3)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC6H4NN)(CO)2(PPh3) 2]BF4 (4) with NaBH4 and 2 in 50% yield. When "Ru(CO)(PPh3)3" generated by the reaction of [RuH2(CO)(PPh3)3] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh3)2(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH4PF6 or H3PW12O40 proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H3PW12O40 as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction.
AB - The reaction of [Ru(CO)2(PPh3)3] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)2(PPh3)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC6H4NN)(CO)2(PPh3) 2]BF4 (4) with NaBH4 and 2 in 50% yield. When "Ru(CO)(PPh3)3" generated by the reaction of [RuH2(CO)(PPh3)3] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh3)2(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH4PF6 or H3PW12O40 proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H3PW12O40 as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction.
KW - Anilines
KW - Hydroamination
KW - Phenylacetylene
KW - Zero-valent ruthenium complexes
KW - o-Styrylphosphine
UR - http://www.scopus.com/inward/record.url?scp=37849187495&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=37849187495&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2006.09.015
DO - 10.1016/j.jorganchem.2006.09.015
M3 - Article
AN - SCOPUS:37849187495
VL - 691
SP - 5739
EP - 5745
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 26
ER -