Recent Advances in Homogeneous Catalysis from Modern NMR Measurements Methoxycarbonylation of Ethene

26 Август 2011, 14:00
ауд. 4104, Химический факультет СПбГУ, Санкт-Петербург, Россия

Этот доклад можно считать первым событием, связанным с организуемым ресурсным центром, поэтому я буду рад, если вы сможете присутствовать на докладе и распространите эту информацию в своих рабочих группах.

Recent Advances in Homogeneous Catalysis from Modern NMR Measurements Methoxycarbonylation of Ethene.

Автор: Brian Heaton (Chemistry Dept., University of Liverpool, UK)


This lecture will review modern spectroscopic methods to elucidate the mechanisms of transition metal homogeneous reactions. Surprisingly, considering the amount of effort that has gone into mechanistic studies of important, industrial catalytic reactions, there are only a few reactions where all the catalytic intermediates have been completely spectroscopically characterised and identified-this lecture will deal with one such reaction.

The efficient, industrial preparation of methyl propanoate is presently the “bottleneck” in the mult-million tonne commercial production of methyl methacrylate. In conjunction with Lucite Int., we have used “in situ” NMR to develop an efficient Pd-catalytic process for the methoxycarbonylation of ethene, the precursor to methyl methacrylate, and have spectroscopically identified all the intermediates in the catalytic cycle; Lucite Int. recently (2008) built a production plant on Jurong Island, Singapore to commercialise this process, which was sold to Mitsubishi Rayon for £1bn.

Избранные статьи:

1. Heaton BT, Iggo JA, Podkorytov IS, Ponomarenko VI, Selivanov SI and Tunik SP, "A rare example of a di-cationic hydrido carbonyl tetra-nuclear cluster, [H2Rh2Pt2(CO)7(PPh3)3]2+". Inorganica Chimica Acta, 2010, 363, 549–554.

2. Heaton BT, Iggo JA, and Femoni MC, Iapalucci MC, Longoni G, Tiozzo C, Zacchini S, "Sn-centred icosahedral Rh carbonyl clusters: synthesis and structural characterization and 13C–{103Rh} HMQC NMR studies". Dalton Transactions, 2007, 3914-3923.

3. Bradd KJ, Heaton BT, Iggo JA, Jacob C, Sampanthar JT and Zacchini S, "Multinuclear NMR Studies of the Products Resulting from the Reaction of Pyridine or 2,2'-Bipyridine with [Rh4(CO)12]". Dalton Transactions 2007, 685-690.

4. Heaton BT, Iggo JA, and Tomashevskaya MM, Tunik SP, Podkorytov IS, Haukka M, Pakkanen TA, Pirila PL and Pursiainen J, "A novel heterobidentate chiral phosphine and its coordination chemistry in transition metal clusters", Journal of Organometallic Chemistry, 2007, 692, 2911-2923.