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Hydroformylation

E-BookEPUB2 - DRM Adobe / EPUBE-Book
702 Seiten
Englisch
Ernst & Sohnerschienen am16.02.20161. Auflage
Filling a gap in the market for an up-to-date work on the topic, this unique and timely book in 2 volumes is comprehensive in covering the entire range of fundamental and applied aspects of hydroformylation reactions.

The two authors are at the forefront of catalysis research, and unite here their expertise in synthetic and applied catalysis, as well as theoretical and analytical chemistry. They provide a detailed account of the catalytic systems employed, catalyst stability and recovery, mechanistic investigations, substrate scope, and technical implementation. Chapters on multiphase hydroformylation procedures, tandem hydroformylations and other industrially applied reactions using syngas and carbon monoxide are also included.

The result is a must-have reference not only for synthetic chemists working in both academic and industrial research, but also for theoreticians and analytical chemists.


Armin Borner studied education and chemistry at the University of Rostock and completed his PhD thesis in the group of Prof. Dr. H. Kristen in 1984. Between 1984 and 1992 he was a scientific co-worker in the field of complex catalysis at the Academia of Science under Prof. Dr. H. Pracejus. After a postdoctoral term in the group of Prof. Dr. H. B. Kagan in Orsay, France, he relocated to the Max-Planck-Group for Asymmetric Catalysis in Rostock in 1993, where he was awarded his professorial research degree (habilitation) in 1995. Since 2000 he has been Professor of Organic Chemistry at the University of Rostock and head of a research department at the Leibniz-Institute for Catalysis (LIKAT) Rostock. His research focuses on applied homogeneous catalysis and he has published over 250 scientific papers, reviews, book chapters and patents. More than 15 catalytic processes and analytical tools which have been developed in his department are running in a technical scale or have been commercialized.

Robert Franke studied chemistry at Bochum University, Germany. He earned his doctorate degree in 1994 in the field of relativistic quantum chemistry under Prof. Dr. W. Kutzelnigg. After working for a period as a research assistant, he joined the process engineering department of the former Huls AG in Germany, a predecessor company of Evonik Performance Materials GmbH, in 1998. He is now Director Innovation Management Hydroformylation. He was awarded his professorial research degree (habilitation) in 2002, since when he has taught at the University of Bochum. In 2011 he was made adjunct professor. His research focuses on homogeneous catalysis, process intensification, and computational chemistry. He has published over 150 scientific papers, reviews, book chapters and patents.

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Produkt

KlappentextFilling a gap in the market for an up-to-date work on the topic, this unique and timely book in 2 volumes is comprehensive in covering the entire range of fundamental and applied aspects of hydroformylation reactions.

The two authors are at the forefront of catalysis research, and unite here their expertise in synthetic and applied catalysis, as well as theoretical and analytical chemistry. They provide a detailed account of the catalytic systems employed, catalyst stability and recovery, mechanistic investigations, substrate scope, and technical implementation. Chapters on multiphase hydroformylation procedures, tandem hydroformylations and other industrially applied reactions using syngas and carbon monoxide are also included.

The result is a must-have reference not only for synthetic chemists working in both academic and industrial research, but also for theoreticians and analytical chemists.


Armin Borner studied education and chemistry at the University of Rostock and completed his PhD thesis in the group of Prof. Dr. H. Kristen in 1984. Between 1984 and 1992 he was a scientific co-worker in the field of complex catalysis at the Academia of Science under Prof. Dr. H. Pracejus. After a postdoctoral term in the group of Prof. Dr. H. B. Kagan in Orsay, France, he relocated to the Max-Planck-Group for Asymmetric Catalysis in Rostock in 1993, where he was awarded his professorial research degree (habilitation) in 1995. Since 2000 he has been Professor of Organic Chemistry at the University of Rostock and head of a research department at the Leibniz-Institute for Catalysis (LIKAT) Rostock. His research focuses on applied homogeneous catalysis and he has published over 250 scientific papers, reviews, book chapters and patents. More than 15 catalytic processes and analytical tools which have been developed in his department are running in a technical scale or have been commercialized.

Robert Franke studied chemistry at Bochum University, Germany. He earned his doctorate degree in 1994 in the field of relativistic quantum chemistry under Prof. Dr. W. Kutzelnigg. After working for a period as a research assistant, he joined the process engineering department of the former Huls AG in Germany, a predecessor company of Evonik Performance Materials GmbH, in 1998. He is now Director Innovation Management Hydroformylation. He was awarded his professorial research degree (habilitation) in 2002, since when he has taught at the University of Bochum. In 2011 he was made adjunct professor. His research focuses on homogeneous catalysis, process intensification, and computational chemistry. He has published over 150 scientific papers, reviews, book chapters and patents.

Details
Weitere ISBN/GTIN9783527677955
ProduktartE-Book
EinbandartE-Book
FormatEPUB
Format Hinweis2 - DRM Adobe / EPUB
FormatFormat mit automatischem Seitenumbruch (reflowable)
Erscheinungsjahr2016
Erscheinungsdatum16.02.2016
Auflage1. Auflage
Seiten702 Seiten
SpracheEnglisch
Dateigrösse47489 Kbytes
Artikel-Nr.3240541
Rubriken
Genre9201

Inhalt/Kritik

Inhaltsverzeichnis
Introduction
Metals in Hydroformylation
Organic Ligands
Syngas and Alternative Syngas Sources
Hydroformylation Reactions
Tandem and other Sequential Reactions using a Hydroformylation Step
Synthesis of Special Products via Hydroformylation
Hydroformylation in Nonconventional Reaction Media
Decarbonylation and Dehydrocarbonylation of Aldehydes
Selected Aspects of Production Processesmehr
Leseprobe
Chapter 1
Metals in Hydroformylation
1.1 The Pivotal Role of Hydrido Complexes

There are very many investigations in the literature concerning the evaluation of different metals and associated organic ligands in hydroformylation. In 2013, Franke and Beller [1] provided a concise summary about the applicability of alternative metals in hydroformylation. In the same year, another survey was assembled by a joint French/Italian cooperation [2]. In order to avoid a full repetition, only some basic conclusions will be mentioned here, which are not in the focus of the reviews cited above.

Several hydrido metal carbonyl complexes are able to catalyze the hydroformylation reaction (Scheme 1.1). Preconditions are the ability for the formation of the relevant intermediates and the passage of crucial steps, such as a metal-alkyl complex by addition of the MâH bond to an olefin (a), subsequent insertion of CO into the M-alkyl bond by migration of a ligated CO ligand (b), and the final hydrogenolysis of the M-acyl bond to liberate the desired aldehyde and to reconstruct the catalyst (c). The type of the transient M-alkyl complex is responsible for the formation of isomeric aldehydes, here distinguished as Cycle I and II. For the successful passage of these catalytic events, besides the reaction conditions the choice of the appropriate metal and its coordinated ligands are pivotal.

Scheme 1.1 Simplified catalytic cycle for hydroformylation.

In the early (mainly patent) literature, besides Co and Rh, Ni, Ir, and other metals of the VIII group, also Cr, Mo, W, Cu, Mn, and even Ca, Mg, and Zn were suggested or claimed for hydroformylation [3]. However, several of them do not exhibit any activity.

Adequate hydroformylation activity of the hydrido carbonyl complexes is attributed to the polarity of the MâH bond [4]. It is assumed that high acidity facilitates the addition to an olefin and the hydrogenolysis of the transient metal-acyl complex in a later stage of the catalytic cycle. In this respect, HCo(CO)4 is a much stronger acid than H2Ru(CO)4, H2Fe(CO)4, H2Os(CO)4, or HMn(CO)5 [5]. Moreover, anionic hydrido complexes, such as [HRu(CO)4]â, behave as strong bases [6]. The conversion of the latter into H2Ru(CO)4 is probably a precondition for the success of the hydroformylation and one explanation why Ru3(CO)12 is more active than [HRu(CO)4]â. The former reacts with H2 to form H2Ru(CO)4 [7]. Low activity was likewise observed for [HOs3(CO)11]â associated with a low thermal stability [8]. Also, [Co(CO)4]â is a poor hydroformylation catalyst [9]. However, with the addition of strong acids, the active species HCo(CO)4 can be generated.

Noteworthy, the instability of HCo(CO)4 under the formation of Co2(CO)8 can be attributed in part to the fast intermolecular elimination of H2. In this manner, also the formation of alkanes can be explained as a key step in the hydrogenation of olefins. On the other hand, the acidic properties of HCo(CO)4 allow the convenient separation of product and catalyst after hydroformylation by conversion into water-soluble Co salts ( decobalting ) [[10]].

Strong acidic metal hydrido complexes such as HCo(CO)4 or complexes with Lewis acid properties, such as Rh2Cl2(CO)4, [Ru(MeCN)3(triphos)](CF3SO3)2, [Pt(H2O)2(dppe)](CF3SO3)2, [Pd(H2O)2(dppe)](CF3SO3)2, or [Ir(MeCN)3(triphos)](CF3SO3)3, are able to act in alcohols as acetalization catalysts, which means they can mediate the transformation of the newly formed aldehydes into acetals (see Section 5.3).

The number of CO ligated to the same metal may affect the catalytic properties (Scheme 1.3) [11]. With cobalt (but also with rhodium) both the tetra and tricarbonyl complexes are considered as catalysts (Scheme 1.2). It is thought that the coordinatively unsaturated complex HCo(CO)3 is more active than HCo(CO)4. Moreover, because of different steric congestions of the metal center, it is assumed that both complexes have different regiodiscriminating propensities for the formation of transient alkyl complexes and, consequently, for the formation of isomeric aldehydes. Therefore, the effects that have been observed at different CO partial pressures can be best explained by assuming the formation of HCo3(CO)9 in a solution containing HCo(CO)4 and its precursor Co2(CO)8 under hydrogen [[12]]. HCo3(CO)9 reacts with hydrogen to form HCo(CO)3 [13]. The latter is more active in isomerization and, consequently, forms more isomeric aldehyde as a final product.

Scheme 1.2 Competition between isomerization and hydroformylation in relation to CO pressure.

In comparison to HCo(CO)4, the rhodium congener has a greater tendency to liberate one CO ligand [14]. In other words, the equilibrium in Scheme 1.3 is less markedly displaced to the left-hand side in comparison to the cobalt-based system.

Scheme 1.3 Equilibrium of catalytically active hydrido carbonyl complexes.

Bearing in mind the greater atomic radius of Rh, it becomes apparent why an unmodified rhodium catalyst generates a greater amount of branched aldehydes in comparison to the cobalt congener. For example, in the hydroformylation of 1-pentene, an l/b ratio of only 1.6 : 1 was found, while with the cobalt complex a ratio of 4 : 1 resulted. A similar correlation has been qualitatively deduced from reactions mediated by the metal clusters Ru3(CO)12, Os3(CO)12, and Ir4(CO)12. Because of the larger atomic radii of the metals, in hydroformylation these catalysts produce more branched aldehydes than observed in the reaction with Co2(CO)8. Unfortunately, most of these results were achieved under different reaction conditions or are difficult to interpret because of low reaction rates and are therefore not strictly comparable.

Polynuclear metal clusters may behave differently in catalysis in comparison to their mononuclear species [15]. Thus, the catalytic activity of [HRu(CO)4]â is superior to that of [HRu3(CO)11]â [6]. Noteworthy, H4Ru4(CO)12 is particularly active in hydroformylation with CO2 [16].

Currently, with unmodified metal carbonyl complexes, the following trend of hydroformylation activity is accepted (ordered by decreasing activity) [17]:

In subsequent chapters, only hydroformylations with Co, Rh, Ru, Pd, Pt, Ir, and Fe will be discussed in detail. Occasionally also molybdenum complexes (e.g., mer-Mo(CO)3(p-C5H4N-CN)3) [18] or osmium complexes (e.g., HOs(κ3-O2CR)(PPh3)2) have been investigated [19]. Only recently, HOs(CO)(PPh3)3Br was evaluated for the hydroformylation of several olefins [20]. A main concern was the high isomerization tendency (up to 39%) noted.
References
1. Pospech, J., Fleischer, I., Franke, R., Buchholz, S., and Beller, M. (2013) Angew. Chem. Int. Ed., 52, 2852-2872.
2. Gonsalvi, L., Guerriero, A., Monflier, M., Hapiot, F., and Perruzzini, M. (2013) Top. Curr. Chem., 342, 1-48.
3. Falbe, J. (1967), and cited literature) Synthesen mit Kohlenmoxid, Springer-Verlag, Berlin.
4. Imjanitov, N.S. and Rudkovskij, D.M. (1969) J. Prakt. Chem., 311, 712-720.
5. Moore, E.J., Sullivan, J.M., and Norton, J.R. (1986) J. Am. Chem. Soc., 108, 2257-2263.
6. Hayashi, T., Gu, Z.H., Sakakura, T., and Tanaka, M. (1988) J. Organomet. Chem., 352, 373-378.
7. Whyman, R. (1973) J. Organomet. Chem., 56, 339-343.
8. Marrakchi, H., Nguini Effa, J.-B., Haimeur, M., Lieto, J., and Aune, J.-P. (1985) J. Mol. Catal., 30, 101-109.
9. Dengler, J.E., Doroodian, A., and Rieger, B. (2011) J. Organomet. Chem., 696, 3831-3835.
10. (a) See e.g.: Gwynn, B.H. and Tucci, E.R. (to Gulf Research & Development Company) (1968) Patent US 3,361,829;(b) Tötsch, W., Arnoldi, D., Kaizik, A., and Trocha, M. (to Oxeno Olefinchemie GmbH) (2003) Patent WO 03/078365.
11. For a detailed discussion, compare: Cornils, B. (1980) in New Syntheses with Carbon Monoxide, Reactivity and Structure, Concepts in Organic Chemistry, vol. 11 (ed. J. Falbe), Springer-Verlag, Berlin, pp. 38-45.
12. (a) Pino, P. (1983) Ann. N.Y. Acad. Sci., 415, 111-128;(b) Pino, P., Major, A., Spindler, F., Tannenbaum, R., Bor, G., and Hórvath, I.T. (1991) J. Organomet. Chem., 417, 65-76.
13. Tannenbaum, R. and Bor, G. (1999) J. Organomet. Chem., 586, 18-22 and ref. cited therein.
14. Marco, L. (1974) in Aspects of Homogeneous Catalysis (ed. R. Ugo), D. Reidel Publishing Company, Dordrecht, Holland; cited in Cornils, B. (1980) in New Syntheses with Carbon Monoxide, Reactivity and Structure, Concepts in Organic Chemistry, vol. 11 (ed. J.,Falbe), Springer-Verlag, Berlin, pp 1-225 as Ref. 75.
15. Fusi, A., Cesarotti, E., and Ugo, R. (1981) J. Mol. Catal., 10, 213-221.
16. Tominaga, K.-i. and Sasaki, Y. (2000) Catal. Commun., 1, 1-3.
17. Pruchnik, F.P. (1990) Organometallic Chemistry of Transition Elements, Plenum Press, New York, p. 691.
18. Suárez, T., Fontal, B., Parra, M.F., Reyes, M., Bellandi, F., Diaz, J.C., Cancines, P., and Fonseca, Y. (2010) Transition Met. Chem., 35, 293-295.
19. Rosales, M., Alvarado, B., Arrieta, F., De La Cruz, C., González, À.,...
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