TY - JOUR
T1 - Homogeneous Catalytic Carbonylation of Nitroaromatics. 8. Kinetic and Mechanistic Studies of the Carbon-Nitrogen Bond and Product Forming Steps from Ru(Ph2PCH2CH2PPh2)(CO)2[C(O)OCH3]2
T2 - The Turnover Limiting Reactions in the Catalytic Cycle
AU - Gargulak, Jerry D.
AU - Gladfelter, Wayne L.
PY - 1994/5/1
Y1 - 1994/5/1
N2 - Mechanistic studies of the reaction of (OC-6-3 2)-dicarbonylbis(methoxycarbonyl)[1, 2-bis(diphenylphosphino)- ethane]ruthenium(II) with p-toluidine to form N, Nʹ-di-p-tolylurea are presented. The overall reaction was studied from 22 to 103 °C and was found to be first order with respect to each reactant. Spectroscopic and kinetic studies between 22 and 52 °C showed that the reaction proceeds through a species, Ru(dppe)(CO)2[C(O)OCH3][C(O)-NH(p-tolyl)], which is in equilibrium with Ru(dppe)(CO)2[C(O)OCH3]2. The mechanism of the C-N bond forming step is proposed to involve nucleophilic attack on a coordinated Ru-CO moiety with subsequent cleavage of the C(O)-OMe bond. The methoxycarbonyl-carbamoyl complex decomposes in a unimolecular fashion to liberate CH3OH, the starting catalyst Ru(dppe)(CO)3, and p-tolyl isocyanate, which is immediately scavenged by excess amine to form N, Nʹ-di-p-tolylurea. Studies of the analogous bis(isopropylcarbamoyl) complex provided supporting evidence for isocyanate elimination. Thermolysis of (OC-6-32)-dicarbonylbis(isopropylcarbamoyl)[l, 2-bis(diphenylphosphino)-ethane]ruthenium(II) yields isopropylamine, the starting catalyst Ru(dppe)(CO)3, and isopropyl isocyanate, which reacts with isopropylamine over time to form diisopropylurea. The kinetics obtained from all of the stoichiometric reactions were combined into a suitable expression and found to lie on the same Arrhenius activation energy plot as the overall rate of the catalytic reaction.
AB - Mechanistic studies of the reaction of (OC-6-3 2)-dicarbonylbis(methoxycarbonyl)[1, 2-bis(diphenylphosphino)- ethane]ruthenium(II) with p-toluidine to form N, Nʹ-di-p-tolylurea are presented. The overall reaction was studied from 22 to 103 °C and was found to be first order with respect to each reactant. Spectroscopic and kinetic studies between 22 and 52 °C showed that the reaction proceeds through a species, Ru(dppe)(CO)2[C(O)OCH3][C(O)-NH(p-tolyl)], which is in equilibrium with Ru(dppe)(CO)2[C(O)OCH3]2. The mechanism of the C-N bond forming step is proposed to involve nucleophilic attack on a coordinated Ru-CO moiety with subsequent cleavage of the C(O)-OMe bond. The methoxycarbonyl-carbamoyl complex decomposes in a unimolecular fashion to liberate CH3OH, the starting catalyst Ru(dppe)(CO)3, and p-tolyl isocyanate, which is immediately scavenged by excess amine to form N, Nʹ-di-p-tolylurea. Studies of the analogous bis(isopropylcarbamoyl) complex provided supporting evidence for isocyanate elimination. Thermolysis of (OC-6-32)-dicarbonylbis(isopropylcarbamoyl)[l, 2-bis(diphenylphosphino)-ethane]ruthenium(II) yields isopropylamine, the starting catalyst Ru(dppe)(CO)3, and isopropyl isocyanate, which reacts with isopropylamine over time to form diisopropylurea. The kinetics obtained from all of the stoichiometric reactions were combined into a suitable expression and found to lie on the same Arrhenius activation energy plot as the overall rate of the catalytic reaction.
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U2 - 10.1021/ja00088a015
DO - 10.1021/ja00088a015
M3 - Article
AN - SCOPUS:0000911196
SN - 0002-7863
VL - 116
SP - 3792
EP - 3800
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 9
ER -