COMPUTATIONAL MODELING OF HOMOGENEOUS CATALYSIS Catalysis by Metal Complexes Volume 25 Editors: Brian James, University of British Columbia, Vancouver, Canada Piet W N M van Leeuwen, University of Amsterdam, The Netherlands Advisory Board: Albert S.C Chan, The Hong Kong Polytechnic University, Hong Kong Robert Crabtee, Yale University, U.S.A David Cole-Hamilton, University of St Andrews, Scotland István Horváth, Eotvos Lorand University, Hungary Kyoko Nozaki, University of Tokyo, Japan Robert Waymouth, Stanford University, U.S.A The titles published in this series are listed at the end of this volume COMPUTATIONAL MODELING OF HOMOGENEOUS CATALYSIS edited by Feliu Maseras Unitat de Química Física, Universitat Autònoma de Barcelona, Bellaterra, Catalonia, Spain and Agustí Lledós Unitat de Qmica Física, Universitat Autònoma de Barcelona, Bellaterra, Catalonia, Spain KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW eBook ISBN: Print ISBN: 0-306-47718-1 1-4020-0933-X ©2002 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©2002 Kluwer Academic Publishers Dordrecht All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: and Kluwer's eBookstore at: http://kluweronline.com http://ebooks.kluweronline.com Contents Contributors vii Acknowledgements ix Preface xi Computational Methods for Homogeneous Catalysis FELIU MASERAS AND AGUSTÍ LLEDĨS Olefin Polymerization by Early Transition Metal Catalysts LUIGI CAVALLO The Key Steps in Olefin Polymerization Catalyzed by Late Transition Metals ARTUR MICHALAK AND TOM ZIEGLER Hydrogenation of Carbon Dioxide SHIGEYOSHI SAKAKI AND YASUO MUSASHI 23 57 79 Catalytic Enantioselective Hydrogenation of Alkenes STEVEN FELDGUS AND CLARK R LANDIS 107 Isomerization of Double and Triple C-C Bonds at a Metal Center ERIC CLOT AND ODILE EISENSTEIN 137 v Contents vi Rhodium Diphosphine Hydroformylation JORGE J CARBÓ, FELIU MASERAS, AND CARLES BO 161 Transition Metal Catalyzed Borations XIN HUANG AND ZHENGYANG LIN 189 Enantioselective Hydrosilylation by Chiral Pd Based Homogeneous Catalysts with First-Principles and Combined QM/MM Molecular 213 Dynamics Simulations ALESSANDRA MAGISTRATO, ANTONIO TOGNI, URSULA RÖTHLISBERGER, AND TOM K WOO Olefin Dihydroxylation THOMAS STRASSNER 253 The Dötz Reaction: A Chromium Fischer Carbene-Mediated Benzannulation Reaction 269 MIQUEL SOLÀ, MIQUEL DURAN, AND MARICEL TORRENT Mechanism of Olefin Epoxidation by Transition Metal Peroxo Compounds 289 NOTKER RÖSCH, CRISTIANA DI VALENTIN, AND ILYA V YUDANOV The Triple Bond Activation by Transition Metal Complexes 325 DJAMALADDIN G MUSAEV, HAROLD BASCH, AND KEIJI MOROKUMA Index 363 Contributors Harold Basch Department of Chemistry, Bar-Ilan University, RamatGan, 52900, Israel Carles Bo Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Pl.Imperial Tarraco, 1, 43005 Tarragona, Spain Luigi Cavallo Dipartimento di Chimica, Università di Salerno, Via Salvador Allende, I-84081, Baronissi (SA) Italy Jorge J Carbó Unitat de Qmica Física, Edifi C.n, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain Eric Clot LSDSMS (UMR 5636), Case courrier 14, Université Montpellier II, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France Miquel Duran Institut de Química Computacional and Departament de Química, Universitat de Girona, E-17071 Girona, Catalonia, Spain Odile Eisenstein LSDSMS (UMR 5636), Case courrier 14, Université Montpellier II, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France Steven Feldgus Department of Chemistry, University of WisconsinMadison, 1101 University Avenue, Madison, WI 53706, USA Xin Huang Deparment of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People’s Republic of China Clark R Landis Department of Chemistry, University of WisconsinMadison, 1101 University Avenue, Madison, WI 53706, USA Zhengyang Lin Deparment of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People’s Republic of China Agustí Lledós Unitat de Qmica Física, Edifici Cn, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain vii viii Contributors Alessandra Magistrato Laboratory of Inorganic Chemistry, Swiss Federal Institute of Technology, ETH Zentrum, CH-8092 Zürich, Switzerland Feliu Maseras Unitat de Química Física, Edifici Cn, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain Artur Michalak Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R Ingardena 3, 30-060 Cracow, Poland Keiji Morokuma Cherry L Emerson Center for Scientific Computation, and Department of Chemistry,Emory University, Atlanta, Georgia, 30322, USA Djamaladdin G Musaev Cherry L Emerson Center for Scientific Computation, and Department of Chemistry,Emory University, Atlanta, Georgia, 30322, USA Yasuo Musashi Information Processing Center, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555 Japan Notker Rösch Institut für Physikalische und Theoretische Chemie, Technische Universität München, 85747 Garching, Germany Ursula Röthlisberger Laboratory of Inorganic Chemistry, Swiss Federal Institute of Technology, ETH Zentrum, CH-8092 Zürich, Switzerland Shigeyoshi Sakaki Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan Miquel Solà Institut de Química Computacional and Departament de Química, Universitat de Girona, E-17071 Girona, Catalonia, Spain Thomas Strassner Institut für Anorganische Chemie, Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany Antonio Togni Laboratory of Inorganic Chemistry, Swiss Federal Institute of Technology, ETH Zentrum, CH-8092 Zürich, Switzerland Maricel Torrent Medicinal Chemistry Dept., Merck Research Laboratories, Merck & Co., West Point PA, USA Cristiana Di Valentin Dipartimento di Scienza dei Materiali, Università degli Studi di Milano-Bicocca, via Cozzi 53, 20125 Milano, Italy Tom K Woo Department of Chemistry, The University of Western Ontario, London, Ontario, Canada, N6A 5B7 Ilya V Yudanov Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia Tom Ziegler Department of Chemistry, University of Calgary, University Drive 2500, Calgary, Alberta, Canada T2N 1N4 Acknowledgements We must first thank all the contributors for their positive response to our call, their dedicated effort and the timely submission of their chapters We must also thank the people at Kluwer Academic Publishers, especially Jan Willem Wijnen and Emma Roberts for their support and patience with our not always fully justified delays We want to finally thank all the graduate students in our group during these last years: Gregori Ujaque, Lourdes Cucurull-Sánchez, Guada Barea, Jorge J Carbó, Jaume Tomàs, Jean-Didier Maréchal, Nicole Dưlker, Maria Besora, Galí Drudis and David Balcells For creating the environment where the research, even the compilation of edited volumes, is a more enjoyable task ix The N-N Triple Bond Activation by Transition Metal Complexes 353 2.4.3.2 Path II.b The second pathway for the reaction leads to complex B21, where the N-H bonds are trans to each other It takes the now familiar path; addition of across the bond, where the original hydrogen atoms are in the and bonds TS B20 for this reaction involves four atoms, and in the active regions and has the typical bond distances: and The last bond length is normal, while typical equilibrium bond distances for the others are, N-H=1.035Å, H-H=0.74Å and H-Zr=1.95Å The barrier height from to B21 is 32.4(24.7) kcal/mol at the TS B20 The ~7 kcal/mol difference in the barrier height is mainly due to B11(A3), which is destabilized more than B20 under the Zr-P constraint Of course, this "destabilization" represents the constraints of the ligand and should give more realistic energetics Thus, 24.7 kcal/mol is the barrier height, which is ~5 and 3.5 kcal/mol higher than the and barriers, respectively The calculated difference is not sufficiently large to rule out this path as experimentally unfeasible TS B20 leads to complex B21 Here, the N-H and Zr-H bonds form a relatively symmetric geometry, moderated by the eclipsed nature of pairs of N-H and Zr-H bonds Thus, is 2.355A and is 2.251 Å The same difference is found for the and bond lengths It should be noted that the bond length is hardly affected in going all three distances being within 0.005Å of each other This has been found and explained for the previous H-H additions across Zr-N The two NH bonds in B21 are trans to each other across the bond This trans conformation does not allow hinging at the axis that would allow a stronger Zr-Zr bonding interaction Therefore, the core in B21 is essentially planar and the Zr-Zr distance is long at 4.353Å This distance can be compared with the corresponding value in A3 (3.697Å) and in B3 (3.558Å) The latter is the product of and is strongly hinged at the axis, which is allowed by the two N-H bonds having the cis conformation Reaction product B21 is calculated to be 12.5(14.4) kcal/mol above This energy difference is higher than B3 relative to and B13 relative to and again indicates that is probably less favorable than and/or The approximate IRC starting from the TS actually leads to B11' (not presented in Figure 8) in the reverse direction B11’(A3’ in the previous section) closely relates to B11 and differs from that mainly by having the bond rotated from being approximately parallel to to approximately perpendicular to and tilted upward towards the cluster on B11' is 1.9(1.3) kcal/mol less stable than B11 The structure B11’, more 354 Djamaladdin G Musaev, Harold Basch, and Keiji Morokuma likely, is an artifact of the simple model for the macrocyclic ligand (for detail see our paper) [13, 14] In any event, given the similarity in structure and energy of B11 and B11', we treat them as equivalent, from the point of view of the reaction path In the forward direction the unconstrained geometry optimization leads directly to B21, but the Zr-P frozen optimization leads to a form of B21 (B21', not shown in Figure 8) having one Zr-H bond rotated away from being eclipsed with an N-H bond towards alignment with the bond axis B21' is ~6 kcal/mol more stable than B21, due to the relief of one eclipsed Zr-H/N-H interaction However, in B21' , the orientation of the ligands on the Zr center with the rotated Zr-H bond has the two groups cis to each other, rather than trans as in the real ligand The B21 structure, although more stable than B21’, would then seem to be an artificial result of the unconnected model in place of the macrocyclic From the reaction path point of view, we treated structures B21 and B21' as the same Therefore, one concludes that the approximate IRC in both the forward and reverse directions from TS B20 leads to B11 (B11') and B21 (B21'), respectively The next stage of the reaction mechanism is the motion connecting B21 with the two bridging N-H bonds trans to each other to B13 with cis N-H bonds B13 is calculated to be more stable than B21 by 16.0 kcal/mol in the Zr-P frozen structures This stabilization can be explained in terms of the stronger Zr…Zr interaction in B13, which also resulted in the “bent” eclipsed conformation Indeed, the Zr…Zr distance is found to be much longer in the staggered conformation than in the eclipsed one The barrier(s) for can be expected to be small As pointed out above, in B13 the core is hinged at the axis Because of this difference between B21 and B13 it is difficult to assess the degree of motion of the ligands, if any, in going from B21 to B13 The Zr-N and N-N bond distances not change much from B21 to B13, as expected from the preservation of all the bond types The Zr-Zr distance decreases from 4.353Å to 3.970Å (B13) due to the hinged bending of the core Thus, the above presented results show that the addition of the second hydrogen molecule to B11 takes place via path II.a, which is kinetically and thermodynamically more favorable than path II.b Indeed, reaction path II.a, occurs only with the 21.3 kcal/mol barrier and is endothermic by 5.6 kcal/mol In contrast, reaction path II.b, requires 24.7 kcal/mol and is endothermic by 14.4 kcal/mol However, in both cases the reverse reactions, and respectively, which occur with only by 15.7 and 10.3 kcal/mol barriers and are exothermic (by 5.9 and 14.4 kcal/mol, respectively) will occur more easily, and the addition of the molecule to complex B11 (A3) has to compete against this process The N-N Triple Bond Activation by Transition Metal Complexes 2.5 355 Addition of the third hydrogen molecule, reaction C The complexes that can be starting points for addition of the next molecule of are B3 (which we call C1), B13(C4) and B21(C7) Because of atomic congestion, only Zr-P frozen structures were optimized for the expected TS’s and products of these reactions 2.5.1 Reaction of complex C1 Let us start our discussion from the reaction of C1 with a dihydrogen molecule As seen in Figure 10, the addition of to C1 occurs across a ZrN bond Reactant C1 has and bonds The third molecule can then attach to the hydrogen-bare and one of the bridging nitrogen atoms in our case) to form a ring As seen in the TS, C2, active site internuclear distances have their usual values: and The last value is somewhat longer than in similar TS’s discussed in earlier sections, probably because of the additional general crowding of a larger number of atoms The bond is elongated to 2.722Å because of the high coordination around The distance is constrained by the active site ring The Zr-Zr distance is 3.579Å, typical for systems with a bridging Zr-H-Zr bond The bond is preserved at 1.456Å The product of reaction is C3 Each Zr atom has a Zr-H bond, but is longer because of stronger bonding of to The bond is broken at 3.312Å, but the bond is maintained at 1.473Å The Zr-Zr distance is essentially unchanged in the transformation The barrier height at C2 is calculated to be a relatively high, 28.8 kcal/mol C3 is calculated to be kcal/mol above reactants 356 Djamaladdin G Musaev, Harold Basch, and Keiji Morokuma The N-N Triple Bond Activation by Transition Metal Complexes 2.5.2 357 Reaction of complex B13 Starting from C4, addition of the third dihydrogen molecule takes place, as expected, across one of the two longer Zr-N bonds As seen in Figure 7, in TS C5, the dihydrogen bond being broken is elongated to 0.865A Meantime the forming and bonds are found to be 1.540Å and 2.256Å, respectively These values of the forming and breaking bonds during the reaction clearly indicate an early (reactant-like) character of TS C5 At C5, the and bond distances have changed only slightly, while, as expected, the and bond distances changed significantly; the first of them is completely broken, while the other is elongated by 0.13Å The bond is preserved at 1.489Å The product C6 has a completely broken bond, but the bond is preserved at 1.482Å has two Zr-H bonds and has only one The reaction is calculated to be 8.7 kcal/mol endothermic The barrier height at C5 is calculated to be 25.5 kcal/mol 2.5.3 Reaction of complex B21 As shown above, C7 has the same type and number of bonds as C4, differs only in conformation, and is 16 kcal/mol less stable than C4(B13) One may expect that the products of reaction C7 and C4 with another molecule also will be different from each other by conformational changes Therefore, we will not discuss the geometries of transition state C8 and product C9 Here, we would only like to point out that the reaction takes place with an 18.1 kcal/mol barrier and is exothermic by 10.0 kcal/mol We did not investigate possible processes starting from C3, C6 and C9 However, we have calculated complex C10 with the core, which can be a result of multiple (or single) rearrangements of complexes C3, C6 and C9 As seen in Figure 10, the main structural features of C10 are two bridging and a terminal hydrogen atom on each Zr-center The calculated N-N distance, 2.638Å, in C10 is significantly longer than that for structures C3, C6 and C9, and thus the N-N bond is completely broken in C10 C10 is calculated to be significantly lower by energy than C3, C6 and C9; for example, it lies about 55.1 kcal/mol lower than C9 In summary, we note that, for B3(C1) and B13(C4), the thermodynamically most favorable products of the addition of two molecule to A1, the calculated barrier heights of reactions with the third molecule are a few kcal/mol larger than those for the first and the second addition processes we reported above Therefore, by adjusting the reaction 358 Djamaladdin G Musaev, Harold Basch, and Keiji Morokuma conditions or by optimizing ligands, the reaction of the third may be possible 2.6 molecule Summary From these studies, one may draw the following conclusions: where The reaction of the model complex, A1, with a hydrogen molecule proceeds via a 21 kcal/mol barrier at the “metathesis-like” transition state, A2, for the H-H bond activation, and produces the diazenidohydride complex, A3, and complex, A7 Complex A7 lies a few kcal/mol lower than A3, and is the only observed product of the experimental analog of the calculated reaction However, the experimentally observed complex, A7, is not the lowest energy structure on the reaction path The hydrazono complex A13 with a bridging and the hydrado complex A17 with two bridging NH units are calculated to be more stable than A7 by about 40-50 kcal/mol However, these complexes cannot be generated by the reaction of at ambient conditions because of very high (nearly 55-60 kcal/mol) barriers at A10 and A14 separating them from A7 The addition of a hydrogen molecule to B1 (the addition of the second to A7), the experimentally observed product of the reaction can take place to give product B3 with a 19.5 kcal/mol barrier, which is 1.2 kcal/mol smaller than that for the reaction Since the addition of the first molecule to A1 is known to occur at laboratory conditions, one predicts that the addition of the second hydrogen molecule to A1 (or the addition of the molecule to B1(A7)) should also be feasible From the product B3, which lies by 5.7 kcal/mol lower than reactants the process will most likely proceed via either channel I.a (the reverse dihydrogen elimination reaction or channel I.b (another dihydrogen elimination process, Both processes have relatively moderate barriers, 25.5 and 35.1 kcal/mol, respectively Path I.c is not feasible because of the high barrier of 41.1(36.1) kcal/mol Later in the sequence of reactions, at complex A15, channel I.b, may split into two new pathways leading to the same product B8 with the core The first pathway, proceeding via N-N bond cleavage leading to A17 and then addition to give B8, is slightly more favorable than the second pathway of direct addition to A15 to give B8 Thus, complex A17, the thermodynamically most stable but kinetically not accessible product of the reaction of The N-N Triple Bond Activation by Transition Metal Complexes 359 A1, with the first is now obtained with the aid of the second reacting hydrogen molecule Reaction of B11(A3) with occurs with a 21.3 kcal/mol barrier, via path II.a and leads to complex B13 or B13’, where the N-H bond are located cis to each other Later, B13 and B13’ which are isomers of the complex B3, rearranges to complex B3, and can follow the path allowed for B3 Present preliminary calculations suggest that addition of the third molecule to A1 is kinetically less favorable than the first two Thus, the findings presented above and their comparison with those available from experiment indicate that addition of the second (and third) hydrogen molecule to complex A1 should be feasible under appropriate laboratory conditions, and formation of ammonia from dinitrogen and dihydrogen molecule could be catalytic process (see Figure 11) We encourage experimentalists to check our theoretical prediction 360 Djamaladdin G Musaev, Harold Basch, and Keiji Morokuma CONCLUDING REMARK In spite of the numerous experimental and theoretical recent developments, the catalytic activation and fixation of the dinitrogen molecule still remains a challenge to chemistry The studies presented above demonstrate that the major problem for dinitrogen activation comes from the high kinetic stability of the triple bond While nature has found a unique way (nitrogenase) to perform this difficult task, scientists are still looking for a breakthrough in this field of the chemistry So far, all the reactions to activate of triple bond under laboratory conditions require the coordination of a molecule to the transition metal centers to form a complex Numerous data suggest that the stronger the bonds the easier bond cleavage, which could occur via various ways including protonation, nucleophilic addition, hydrogenation and coordination of another transition metal center However, the strong bond also makes dinitrogen fixation extremely difficult because of the difficulties in utilization of the formed bond Therefore, the search for new and efficient ways for utilization of a strong bond becomes one of the important tasks Another important and more effective way could be insertion of the ligand into a M-L bond, which requires comprehensive studies In the solution of these problems the close collaboration of experimentalists and theoreticians is absolutely necessary For example, the above presented theoretical results and comparison of those with available experiment clearly indicate that addition of the second (and third) hydrogen molecule to complex A1 should be feasible under appropriate laboratory conditions, and formation of ammonia from dinitrogen and dihydrogen molecules could be a catalytic process (see Figure 11) This conclusion should be tested by experimentalists REFERENCES (a) Howard, J B.; Rees, D C Chem.Rev 1996, 96 , 2965-2982 (b) Burgess, B K.; Lowe, D J Chem.Rev 1996, 96, 2983-3011 (c) Eady, R R Chem.Rev 1996, 96, 30133030 (d) Eady, R R Adv Inorg Chem 1991, 36 , 77 (e) Kim, J.; Rees, D C Nature 1992, 360, 553 (f) Kim, J.; Rees, D C Science 1992, 257, 1677 (g) Dees, D C.; Chan, M K.; Kim, J Adv Inorg Chem 1993, 40, 89 Ertl, G in Catalytic Ammonia Synthesis, Jennings, J.R Eds., Plenum, New York, 1991 See: (a) Leigh, G.J New J Chem 1994, 18, 157-161; (b) Leigh, G.J Science 1998, 279, 506-508, and references therein Vol’pin, M.E.; Shur, V.B Doklady Acad Nauk SSSR 1964, 156, 1102 Bazhenova, T.A.; Shilov, A.E Coord Chem Rev 1995, 144, 69 The N-N Triple Bond Activation by Transition Metal Complexes 10 11 12 13 14 15 16 17 18 19 20 361 (a) Laplaza, C E.; Cummins, C C Science 1995, 268, 861 (b) Laplaza, C E.; Johnson, M J A.; Peters, J C.; Odom, A L.; Kim, E.; Cummins, C C.; George, G N.; Pickering, I J J Am Chem Soc 1996, 118, 8623 (c) Laplaza, C E.; Odom, A L.; Davis, W M.; Cummins, C C J Am Chem Soc 1995, 117, 4999-5000 See: Hidai, M.; Ishii, Y Bull Chem Soc Jpn 1996, 69, 819-831, and references therein Nishibayashi, Y.; Iwai, S.; Hidai, M Science 1998, 279, 540-542 Fryzuk, M D.; Love, J B.; Rettig, S J.; Young, V G Science 1997, 275, 1445-1447 a) Fryzuk, M D.; Haddad, T S.; Rettig, S J J Am Chem Soc 1990, 112, 8185 (b) Fryzuk, M D.; Haddad, T S.; Mylvaganam, M.; McConville, D H.; Rettig, S J J Am Chem Soc 1993, 115, 2782 (c) Cohen, J D.; Mylvaganam, M.; Fryzuk, M D.; Loehr, T M J Am Chem Soc 1994, 116, 9529 (d) Fryzuk, M D.; Love, J B.; Rettig, S J Organometallics 1998, 17, 846 (a) Musaev, D G Russ J Inorg Chem 1988, 33, 3207 (b) Bauschlicher, C W., Jr.; Pettersson, L G M.; Siegbahn, P E M J Chem Phys 1987, 87, 2129 (c) Siegbahn, P.E M J Chem Phys 1991, 95, 364 (d) Blomberg, M R A.; Siegbahn, P E M J Am Chem Soc 1993, 115, 6908 Basch, H.; Musaev, D G.; Morokuma, K.; Fryzuk, M D.; Love, J B.; Seidel, W W.; Albinati, A.; Koetzle, T F.; Klooster, W T.; Mason, S A.; Eckert, J J Am Chem Soc 1999, 121, 523-528 Basch, H.; Musaev, D G.; Morokuma, K J Am Chem Soc 1999, 121, 5754-5761 Basch, H.; Musaev, D G.; Morokuma, K Organometallics 2000, 19, 3393-3403 (a) Becke, A D Phys Rev A 1988, 38, 3098 (b) Becke, A D J Chem Phys., 1993, 98, 5648 (c) Lee, C.; Yang, W.; Parr, R G Phys Rev., 1988, B37, 785 (d) Stephens, P J.; Devlin, F J.; Chabalowski, C F.; M J Frisch, M J., J Phys Chem., 1994, 98, 11623 Frisch, M J et al Gaussian 94, Gaussian, Inc.: Pittsburgh PA, USA, 1995 (a) Stevens, W J.; Basch, H.; Krauss, M J Chem Phys 1984, 81, 6026 (b) Stevens, W J.; Krauss, M.; Basch, H.; Jasien, P G Can J Chem 1992, 70, 612 (a) Serron, S.; Nolan, S P.; Moloy, K G Organometallics 1996, 15, 4301 (b) Serron, S.; Luo, L.; Stevens, E D.; Nolan, S P.; Jones, N L.; Fagan, P J Organometallics 1996, 15, 5209 Yates, B.; Musaev, D G.; Basch, H.; Morokuma, K to be published Basch, H.; Musaev, D G.; Morokuma, K.; Fryzuk, M D.; Love, J B.; Seidel, W W.; Albinati, A.; Koetzle, T F.; Klooster, W T.; Mason, S A.; Eckert, J J Am Chem Soc 1999, 121, 523-528 This Page Intentionally Left Blank Index metathesis 97, 197, 204, 341, 355 [2+2] pathway 255, 260 [3+2] pathway 255, 260 1,3 hydrogen shift 145 activation of N-N triple bond 326 agostic complexes 156 agostic interactions 27, 30, 38, 43, 150, 195, 201 alkene to carbene isomerization 149 alkyne to vinylidene isomerization 141, 146 alkynyl hydride complex 144 allyl ligand 231, 238, 245 allylic alcohol epoxidation 305 anti-lock-and-key mechanism 110, 121 atactic polymers 47 B3LYP method 9, 30, 34, 92, 96, 98, 102, 115, 146, 206, 260, 329 B3PW91 method 139, 150 basis set superposition error 34 benzoxantphos ligand 176 bimolecular hydrogen shift 145 bis-imine ligands 60 BisP* ligand 131 bite angle 175, 182 BLYP method 9, 42 Boltzmann distribution 178 BP86 method 9, 30, 35, 38, 40, 45, 167, 169 BPW91 method 40 branched aldehyde 168, 180 branched polymer 68 bridging hydride ligand 338 Brookhart catalysts 57 carbene ligand 149, 269, 275 Car-Parrinello method 17, 28, 39, 249 CASPT2 method 9, 16 CASSCF method CCSD(T) method 8, 30, 41, 92, 164 cinchona ligands 255 cinnamic acid 260 cobalt catalysts 163 cobalt complexes 145 combinatorial chemistry 18 copper complexes 85 counterion effects 35 coupling of with acetylene 84 cycloaddition 270 C-H complexes 147, 151 chain growing 61, 63 chain termination 61, 65 Chalk-Harrod mechanism 224 charge decomposition analysis 129 chelation effect 36 chromium catalysts 265, 275, 295 density functional theory 6, 9, 29, 33, 37, 163, 199, 257, 275, 293 See also B3LYP method, B3PW91 method, BLYP method, BP86 method, BPW91 method diazenidohydride complex 336 diboration 206 dihydrogen elimination 345 DiPAMP ligand 109 DIPHOS ligand 168 diphosphine ligands 109, 166, 173, 328 direct attack of peroxo 297, 301 dissociation of CO 273, 275 dissociation of phosphine 102, 195, 206 dissociation of pyrazole 228 Dötz reaction 269 DuPHOS ligand 112, 118, 124 363 Index 364 dynamic electron correlation effect of phosphine basicity 168 electrochemical reduction of 83 electron correlation electronic effects 13, 44, 219 enamide 115, 118, 124 enantioselectivity 107, 118, 239, 259 extended Hückel method 2, 28, 141, 256, 274, 292 formamidoacrylonitrile 115, 118 frontier orbitals 3, 27, 36, 83, 87, 96, 99, 128, 140, 302 GGA functionals GVB method 8, 29 hafnium complexes 28 Hartree-Fock method 5, 28, 33, 86, 90, 256 homoxantphos ligand 176 hydride pathway for hydrogenation 110 hydroboration 189 hydroformylation 161 hydrogen bonds 308 hydrogen uptake 335, 342, 349 hydrogenation of 79 hydroperoxo ligand 312, 315 hydrosilylation 214 IMOMM method 14, 145, 175, 219 indenyl ligands 49 insertion of acetylene 276 insertion of alkyne 147 insertion of CO 165, 273 insertion of 85 insertion of olefin 36, 45, 61, 63, 88, 150, 173, 178, 195, 201, 230, 297 intraligand H shift 142 intrinsic reaction coordinate 167 IR spectra 170 isomerization of carbene 137 isomerization of growing chain 67 isomerization of vinylcarbene 279 isomerization of vinylidene 137 isotactic polymers 47 keto-enol tautomerization 279 kinetic isotope effects 258, 260 linear aldehyde 168, 180 linear polymer 68 linear/branched ratio 181 localized molecular orbitals 142 manganese catalysts 259 metal-alcoholate complex 307 metallocene ligands 26 methyltrioxorhenium 300 migration of CO 279, 282 migration of hydride 339, 347 molecular dynamics 17, 226 molecular hydrogen complexes 116 molecular mechanics 11, 48, 114 molybdenum catalysts 292, 295, 315 MP2 method 8, 28, 33, 40, 43, 92, 95, 98, 101, 114, 142, 145, 164, 195, 204 MP4 method 41, 92, 167, 204 natural bond orbital 314 nickel catalysts 57, 61 niobium complexes 143 nitrile-substituted enamide 124 nitrogen fixation 326 non dynamic electron correlation 8, 16 non local DFT olefin dihydroxylation 253 olefin epoxidation 289 olefin hydrogenation 107 olefin pathway for hydrogenation 110 olefin polymerization 23, 57 olefin uptake 32, 61, 63, 205, 228 ONIOM method 14, 119, 125, 173 orbital effects 176, 183 organoboranes 189 organosilicon compounds 214 osmium catalysts 254 osmium complexes 148 osmium tetraoxide 254 oxetane complex 256 oxidative addition of alkyne 141 oxidative addition of B-H 195, 206 oxidative addition of C-H 145 oxidative addition of hydrogen 117, 165 oxo process 162 Index palladium catalysts 57, 72, 208, 227 palladium complexes 217 PCM method 17, 264 permanganate 259 peroxo ligand 289, 295 ligand 170 PHANEPHOS ligand 131 platinum catalysts 206 PM3(tm) method polarization functions 41 propylene polymerization 68 pyrazole ligand 303 QM/MM methods 13, 62, 119, 125, 145, 172, 226, 249, 259 See also IMOMM method, ONIOM method QM-guided molecular mechanics 13 quadrant diagrams 122, 127 reductive elimination 94, 118, 201, 234, 273 regioselectivity 44, 66, 166, 181, 233, 237 rhenium catalysts 264, 300 rhodium catalysts 101, 115, 118, 124, 164, 166, 173, 176, 192 rhodium complexes 90, 95, 98, 144, 145 ring closure 273 ruthenium catalysts 102 ruthenium complexes 92, 96, 142, 147, 150, 154, 156 samarium catalysts 204 scandium complexes 30 semiempirical methods 4, 293 solvent effects 17, 34, 165, 263, 303 spin crossing 16 square planar geometry 222 steric effects 13, 44, 62, 180, 219, 230, 259 stochastic simulation 68 substituted enamides 128 syndiotactic polymers 47 tetrahedral distortion 223 tetrapodal phosphine ligand 146 thioboration 208 365 thixantphos ligands 170 time-dependent DFT 16 titanium catalysts 28, 37, 45, 312 trans influence 220 transition metal complexes 82 trichlorosilyl ligand 217 tungsten catalysts 295 tungsten complexes 144 vinyl ether 155 Wilkinson catalyst 108, 190, 192 xantphos-type ligands 174 method Ziegler-Natta polymerization 25 zirconium catalysts 35, 39, 48, 328 zirconium complexes 28 Catalysis by Metal Complexes Series Editors: R Ugo, University of Milan, Milan, Italy B.R James, University of British Colombia, Vancouver, Canada F.J McQuillin: Homogeneous Hydrogenation in Organic Chemistry 1976 ISBN 90-277-0646-8 P.M Henry: Palladium Catalyzed Oxidation of Hydrocarbons 1980 ISBN 90-277-0986-6 R.A Sheldon: Chemicals from Synthesis Gas Catalytic Reactions of CO and 1983 ISBN 90-277-1489-4 W Keim (ed.): Catalysis in A.E Shilov: Activation of Saturated Hydrocarbons by Transition Metal Complexes 1984 ISBN 90-277-1628-5 F.R Hartley: Supported Metal Complexes A New Generation of Catalysts 1985 ISBN 90-277-1855-5 Y Iwasawa (ed.): Tailored Metal Catalysts 1986 G Strukul (ed.): Catalytic Oxidations with Hydrogen Peroxide as Oxidant 1993 ISBN 0-7923-1771-8 10 A Mortreux and F Petit (eds.): Industrial Applications of Homogeneous Catalaysis 1988 ISBN 90-2772-2520-9 11 N Farrell: Transition Metal Complexes as Drugs and Chemotherapeutic Agents 1989 ISBN 90-2772-2828-3 12 A.F Noels, M Graziani and A.J Hubert (eds.): Metal Promoted Selectivity in Organic Synthesis 1991 ISBN 0-7923-1184-1 13 L.I Simándi (ed.): Catalytic Activation of Dioxygen by Metal Complexes 1992 ISBN 0-7923-1896-X 14 K Kalyanasundaram and M Grätzel (eds.): Photosensitization and Photocatalysis ISBN 0-7923-2261-4 Using Inorganic and Organometalic Compounds 1993 15 P.A Chaloner, M.A Esteruelas, F Joó and L.A Oro: Homogeneous Hydrogenation 1994 ISBN 0-7923-2474-9 16 G Braca (ed.): Oxygenates by Homologation or CO Hydrogenation with Metal Complexes 1994 ISBN 0-7923-2628-8 17 F Montanari and L Casella (eds.): Metalloporphyrins Catalyzed Oxidations 1994 ISBN 0-7923-2657-1 Chemistry 1983 ISBN 90-277-1527-0 ISBN 90-277-1866-0 R.S Dickson: Homogeneous Catalysis with Compounds of Rhodium and Iridium 1985 ISBN 90-277-1880-6 18 P.W.N.M van Leeuwen, K Morokuma and J.H van Lenthe (eds.): Theoretical Aspects of Homogeneous Catalisis Applications of Ab Initio Molecular Orbital Theory 1995 ISBN 0-7923-3107-9 19 T Funabiki (ed.): Oxygenates and Model Systems 1997 20 S Cenini and F Ragaini: Catalytic Reductive Carbonylation of Organic Nitro Compounds 1997 ISBN 0-7923-4307-7 21 A.E Shilov and G.P Shul’pin: Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes 2000 ISBN 0-7923-6101-6 22 P.W.N.M van Leeuwen and C Claver (eds.): Rhodium Catalyzed Hydroformylation 2000 ISBN 0-7923-6551-8 23 F Joó: Aqueous Organometallic Catalysis 2001 24 R.A Sánchez-Delgado: Organometallic Modeling of the Hydrodesulfurization and Hydrodenitrogenation Reactions 2002 ISBN 1-4020-0535-0 25 F Maseras and A Lledós (eds.): Computational Modeling of Homogeneous Catalysis 2002 ISBN 1-4020-0933-X ISBN 0-7923-4240-2 ISBN 1-4020-0195-9 KLUWER ACADEMIC PUBLISHERS – BOSTON / DORDRECHT / LONDON * Volume is previously published under the Series Title: Homogeneous Catalysis in Organic and iNorganic Chemistry ... compilation of edited volumes, is a more enjoyable task ix Preface This book presents an updated account on the status of the computational modeling of homogeneous catalysis at the beginning of the... University of Tokyo, Japan Robert Waymouth, Stanford University, U.S.A The titles published in this series are listed at the end of this volume COMPUTATIONAL MODELING OF HOMOGENEOUS CATALYSIS. . .COMPUTATIONAL MODELING OF HOMOGENEOUS CATALYSIS Catalysis by Metal Complexes Volume 25 Editors: Brian James, University of British Columbia, Vancouver, Canada