Abstract
In this chapter, a perspective on how the field of applied computational organometallic chemistry has developed since the mid-1980s is presented. We describe the way in which the modelling of chemical systems has evolved over time, using metallocene chemistry as an example, and highlight the successes and limitations of simple models that were mandatory in the early days of the discipline. A number of more recent case studies are then presented where the full experimental system is now employed and a more quantitative outcome is sought. This includes examples from the Ce-mediated hydrogenation of pyridine, Rh-catalysed C–H bond activation and functionalization, Pd-catalysed azidocarbonylation and phenyl iodide activation at Ru(II) complexes. We conclude with our take on the title question.
Keywords
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsReferences
Woodward RB, Hoffmann R (1965) Stereochemistry of electrocyclic reactions. J Am Chem Soc 87:395–397
Woodward RB, Hoffmann R (1965) Selection rules for concerted cycloaddition reactions. J Am Chem Soc 87:2046–2048
Woodward RB, Hoffmann R (1965) Selection rules for sigmatropic sections. J Am Chem Soc 87:2511–2513
Woodward RB, Hoffmann R (1969) The conservation of orbital symmetry. Angew Chem Int Ed Engl 8:781–932
Fukui K (1982) The role of frontier orbitals in chemical reactions. Angew Chem Int Ed Engl 21:801–809
Hoffmann R (1982) Building bridges between inorganic and organic chemistry. Angew Chem Int Ed Engl 21:711–724
Cramer CJ, Truhlar DG (2009) Density functional theory for transition metals and transition metal chemistry. Phys Chem Chem Phys 11:10757–10816
Becke AD (2014) Perspective: fifty years of density-functional theory in chemical physics. J Chem Phys 140:18A301
Appelhans LN, Zuccaccia D, Kovacevic DA, Chianese AR, Miecznikowski JR, Macchioni A, Clot E, Eisenstein O, Crabtree RH (2005) An anion-dependent switch in selectivity results from a change of C-H activation mechanism in the reaction of an imidazolium salt with IrH5(PPh3)2. J Am Chem Soc 127:16299–16311
Leduc A-M, Salameh A, Soulivong D, Chabanas M, Basset J-M, Copéret C, Solans-Monfort X, Clot E, Eisenstein O, Böhm VPW, Röper M (2008) β-H transfer from the metallacyclobutane: a key step in the deactivation and byproduct formation for the well-defined silica-supported rhenium alkylidene alkene metathesis catalyst. J Am Chem Soc 130:6288–6297
Erhardt S, Grushin VV, Kilpatrick AH, Macgregor SA, Marshall WJ, Roe DC (2008) Mechanisms of catalyst poisoning in palladium-catalyzed cyanation of haloarenes. Remarkably facile C-N bond activation in the [(Ph3P)4Pd]/[Bu4N]+ CN− system. J Am Chem Soc 130:4828–4845
Crabtree RH (2012) Resolving heterogeneity problems and impurity artifacts in operationally homogeneous transition metal catalysts. Chem Rev 112:1536–1554
Basch H, Musaev DG, Morokuma K, Fryzuk MD, Love JB, Seidel WW, Albinati A, Koetzle TF, Klooster WT, Mason SA, Eckert J (1999) Theoretical predictions and single-crystal neutron diffraction and inelastic neutron scattering studies on the reaction of dihydrogen with the dinuclear dinitrogen complex of zirconium [P2N2]Zr(μ-η2-N2)Zr[P2N2], P2N2 = PhP(CH2SiMe2NSiMe2CH2)2PPh. J Am Chem Soc 121:523–528
Lauher JW, Hoffmann R (1976) Structure and chemistry of bis(cyclopentadienyl)-MLn complexes. J Am Chem Soc 98:1729–1742
Thomas JR, Quelch GE, Seidl ET, Schaefer HF III (1992) The titane molecule (TiH4): equilibrium geometry, infrared and Raman spectra of the first spectroscopically characterized transition metal tetrahydride. J Chem Phys 96:6857–6861
Maron L, Eisenstein O, Alary F, Poteau R (2002) Modeling C5H5 with atoms or effective group potential in lanthanide complexes: isolobality not the determining factor. J Phys Chem A 106:1797–1801
Steigerwald ML, Goddard WA III (1984) 2s + 2s Reactions at transition metals. 1. The reactions of D2 with Cl2TiH+, Cl2TiH, and Cl2ScH. J Am Chem Soc 106:308–311
Maron L, Eisenstein O (2000) Do f Electrons play a role in the lanthanide–ligand bonds? A DFT study of Ln(NR2)3; R = H, SiH3. J Phys Chem A 104:7140–7143
Castro L, Kefalidis CE, McKay D, Essafi S, Perrin L, Maron L (2014) Theoretical treatment of one electron redox transformation of small molecule using f-element complexes. Dalton Trans 43:12124–12134
Maron L, Eisenstein O (2001) DFT Study of H–H Activation by Cp2LnH d 0 Complexes. J Am Chem Soc 123:1036–1039
Maron L, Perrin L, Eisenstein O (2002) DFT study of CH4 activation by d 0 Cl2LnZ (Z = H, CH3) complexes. J Chem Soc Dalton Trans 534–539
Perrin L, Maron L, Eisenstein O (2002) A DFT study of SiH4 activation by Cp2LnH. Inorg Chem 41:4355–4362
Perrin L, Maron L, Eisenstein O (2004) Lanthanide complexes: electronic structure and H-H, C-H and Si-H bond activation from a DFT perspective. In: Goldberg KI, Goldman AS (eds) Activation and functionalization of C-H bonds. ACS Symposium Series 885, pp 116–133
Eisenstein O, Maron L (2002) DFT studies of some structures and reactions of lanthanides complexes. J Organomet Chem 647:190–197
Barthelat JC, Chaudret B, Daudey JP, De Loth P, Poilblanc R (1991) Theoretical calculations on Nb and Ta trihydride complexes. Relations with the problem of quantum mechanical exchange coupling. J Am Chem Soc 113:9896–9898
Camanyes S, Maseras F, Moreno M, Lledós A, Lluch JM, Bertrán J (1996) Theoretical study of the hydrogen exchange coupling in the metallocene trihydride complexes [(C5H5)2MH3]n+ (M = Mo, W, n =1; M = Nb, Ta, n = 0). J Am Chem Soc 118:4617–4621
Hyla-Kryspin I, Silverio SJ, Niu S, Gleiter R (1997) An ab initio investigation of σ-bond metathesis and insertion reactions of acetylene with Cl2ZrH+ and Cl2ZrCH3 +. J Mol Cat A Chem 115:183–192
Folga E, Ziegler T (1992) A theoretical study on the activation of hydrogen–hydrogen and hydrogen–alkyl bonds by electron-poor early transition metals. Can J Chem 70:333–342
Watson PL, Parshall GW (1985) Organolanthanides in catalysis. Acc Chem Res 18:51–56
Zachmanoglou CE, Docrat A, Bridgewater BM, Parkin G, Brandow CG, Bercaw JE, Jardine CN, Lyall M, Green JC, Keister JB (2002) The electronic influence of ring substituents and ansa bridges in zirconocene complexes as probed by infrared spectroscopic, electrochemical and computational studies. J Am Chem Soc 124:9525–9546
Ziegler T, Folga E, Berces A (1993) A Density functional study on the activation of hydrogen-hydrogen and hydrogen-carbon bonds by Cp2Sc-H and Cp2Sc-CH3. J Am Chem Soc 115:636–646
Barros N, Eisenstein O, Maron L (2006) DFT studies of the methyl exchange reaction between Cp2M–CH3 or Cp*2M-CH3 (Cp = C5H5, Cp* = C5Me5, M = Y, Sc, Ln) and CH4. Does M ionic radius control the reaction? Dalton Trans 3052–3057
Ziegler T, Folga E (1994) A density functional study on σ-bond metathesis reactions of possible importance in dehydrogenative silane polymerization. J Organomet Chem 478:47–65
Perrin L, Eisenstein O, Maron L (2007) Chemoselectivity in σ bond activations by lanthanocene complexes from a DFT perspective: reactions of Cp2LnR (R = CH3, H, SiH3) with SiH4 and CH3-SiH3. New J Chem 31:549–555
Perrin L, Maron L, Eisenstein O, Tilley TD (2009) Bond activations of PhSiH3 by Cp2SmH: a mechanistic investigation by the DFT method. Organometallics 28:3767–3775
Werkema EL, Messines E, Perrin L, Maron L, Eisenstein O, Andersen RA (2005) Hydrogen for fluorine exchange in CH4-xFx by monomeric [1,2,4-(Me3C)3C5H2]2CeH: experimental and computational studies. J Am Chem Soc 127:7781–7795
Maron L, Perrin L, Eisenstein O (2003) CF4 defluorination by Cp2Ln-H: a DFT study. Dalton Trans 22:4313–4318
Werkema EL, Andersen RA, Yahia A, Maron L, Eisenstein O (2009) Hydrogen for X-group exchange in CH3X (X = Cl, Br, I, OMe, and NMe2) by monomeric [1,2,4-(Me3C)3C5H2]2CeH: experimental and computational support for a carbenoid mechanism. Organometallics 28:3173–3185
Werkema EL, Yahia A, Maron L, Eisenstein O, Andersen RA (2010) Bridging silyl groups in σ-bond metathesis and [1,2]-shifts. Experimental and computational study of the reaction between cerium metallocenes and MeOSiMe3. Organometallics 29:5103–5110
Werkema EL, Yahia A, Maron L, Eisenstein O, Andersen RA (2010) Splitting a C–O bond in dialkylethers with bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium does not occur by a σ-bond pathway: a combined experimental and DFT computational study. New J Chem 34:2189–2196
Werkema EL, Castro L, Maron L, Eisenstein O, Andersen RA (2013) Cleaving bonds in CH3OSO2CF3 with [1,2,4-(Me3C)3C5H2]2CeH; an experimental and computational study. New J Chem 37:132–142
Werkema EL, Castro L, Maron L, Eisenstein O, Andersen RA (2012) Selectivity in the C–H activation reaction of CH3OSO2CH3 with [1,2,4-(Me3C)3C5H2]2CeH or [1,2,4-(Me3C)3C5H2][1,2-(Me3C)2-4-(Me2CCH2)C5H2]Ce: to choose or not to choose. Organometallics 31:870–881
Maron L, Werkema EL, Perrin L, Eisenstein O, Andersen RA (2005) Hydrogen for fluorine exchange in C6F6 and C6F5H by monomeric [1,3,4-(Me3C)3C5H2]2CeH: experimental and computational studies. J Am Chem Soc 127:279–292
Werkema EL, Andersen RA (2008) Fluorine for hydrogen exchange in the hydrofluorobenzene derivatives C6H x F(6-x), where x = 2, 3, 4 and 5 by monomeric [1,2,4-(Me3C)3C5H2]2CeH: the solid state isomerization of [1,2,4-(Me3C)3C5H2]2Ce(2,3,4,5-C6HF4) to [1,2,4-(Me3C)3C5H2]2Ce(2,3,4,6-C6HF4). J Am Chem Soc 130:7153–7165
McKay D, Riddlestone IM, Macgregor SA, Mahon MF, Whittlesey MK (2015) A mechanistic study of Ru-NHC catalysed hydrodefluorination of fluoropyridines: the influence of the NHC on the regioselectivity of C-F activation and chemoselectivity of C-F vs C-H bond cleavage. ACS Catal 5:776–787
Werkema EL, Andersen RA, Maron L, Eisenstein O (2010) The reaction of bis(1,2,4-tri-t-butylcyclopentadienyl)ceriumbenzyl, Cp′2CeCH2Ph, with methylhalides: a metathesis reaction that does not proceed by a metathesis transition state. Dalton Trans 39:6648–6660
Scherer E, Cramer CJ (2003) Quantum chemical characterization of methane metathesis in L2MCH3 (L = H, Cl, Cp, Cp*; M = Sc, Y, Lu). Organometallics 22:1682–1689
Woodrum NL, Cramer CJ (2006) Density functional characterization of methane metathesis with Cp*2MR (M = Sc, Y, Lu; R = Me, tBuCH2). Structural and kinetic consequences of alkyl steric bulk. Organometallics 25:68–73
Barros N, Eisenstein O, Maron L, Tilley TD (2006) DFT investigation of the catalytic hydromethylation of α-olefins by metallocenes. 1. Differences between scandium and lutetium in propene hydromethylation. Organometallics 25:5699–5708
Barros N, Eisenstein O, Maron L, Tilley TD (2008) DFT investigation of the catalytic hydromethylation of olefins by scandocenes. 2. Influence of the ansa ligand on propene and isobutene hydromethylation. Organometallics 27:2252–2257
Barros N, Eisenstein O, Maron L (2010) Catalytic hydrosilylation of olefins with organolanthanides: a DFT study. Part I: hydrosilylation of propene by SiH4. Dalton Trans 39:10749–10756
Barros N, Eisenstein O, Maron L (2010) Catalytic hydrosilylation of olefins with organolanthanide complexes: a DFT study. Part II: influence of the substitution on olefin and silane. Dalton Trans 39:10757–10767
Harvey JN (2010) Ab initio transition state theory for polar reactions in solution. Faraday Discuss 145:487–505
Plata RE, Singleton DA (2015) A case study of the mechanism of alcohol-mediated Morita-Baylis-Hillman reactions. The importance of experimental observations. J Am Chem Soc 137:3811–3826
Perrin L, Werkema EL, Eisenstein O, Andersen RA (2014) Two [1,2,4-(Me3C)3C5H2]2CeH molecules are involved in the hydrogenation of pyridine to piperidine as shown by experiments and calculations. Inorg Chem 53:6361–6373
Deelman BJ, Stevels WM, Teuben JH, Lakin MT, Spek AL (1994) Insertion chemistry of yttrium complex Cp*2Y(2-pyridyl) and molecular structure of an unexpected CO insertion product (Cp*2Y)2(μ-η2:η2-OC(NC5H4)2). Organometallics 13:3881–3891
Evans WJ, Meadows JH, Hunter WE, Atwood JL (1984) Organolanthanide and organoyttrium hydride chemistry. 5. Improved synthesis of [(C5H4R)2YH(THF)]2 complexes and their reactivity with alkenes, alkynes, 1,2-propadiene, nitriles, and pyridine, including structural characterization of an alkylideneamido product. J Am Chem Soc 106:1291–1300
Werkema EL, Maron L, Eisenstein O, Andersen RA (2007) Reactions of monomeric [1,2,4-(Me3C)3C5H2]2CeH and CO with or without H2: an experimental and computational study. J Am Chem Soc 129:2529–2541
Grimme S, Ehrlich S, Goerigk L (2011) Effect of the damping function in dispersion corrected density functional theory. J Comput Chem 32:1456–1465
Grimme S, Steinmetz M (2013) Effects of London dispersion correction in density functional theory on the structures of organic molecules in the gas phase. Phys Chem Chem Phys 15:16031–16042
Hansen A, Bannwarth C, Grimme S, Petrović P, Werlé C, Djukic J-P (2014) The thermochemistry of london dispersion-driven transition metal reactions: getting the ‘right answer for the right reason’. ChemistryOpen 3:177–189
Brandenburg JG, Bender G, Ren J, Hansen A, Grimme S, Eckert H, Daniliuc CG, Kehr G, Erker G (2014) Crystal packing induced carbon–carbon double–triple bond isomerization in a zirconocene complex. Organometallics 33:5358–5364
Moellmann J, Grimme S (2013) Influence of crystal packing on an organometallic ruthenium(IV) complex structure: the right distance for the right reason. Organometallics 32:3784–3787
Carr KJT, Davies DL, Macgregor SA, Singh K, Villa-Marcos B (2014) Metal control of selectivity in acetate-assisted C-H bond activation: an experimental and computational study of heterocyclic, vinylic and phenylic C(sp2)-H bonds at Ir and Rh. Chem Sci 5:2340–2346
Ling L, Brennessel WW, Jones WD (2009) C–H activation of phenyl imines and 2-phenylpyridines with [Cp*MCl2]2 (M = Ir, Rh): regioselectivity, kinetics, and mechanism. Organometallics 28:3492–3500
Algarra AG, Cross WB, Davies DL, Khamker Q, Macgregor SA, McMullin CL, Singh K (2014) Combined experimental and computational investigations of rhodium- and ruthenium-catalyzed C-H functionalization of pyrazoles with alkynes. J Org Chem 79:1954–1970
Algarra AG, Macgregor SA, Panetier JA (2013) Mechanistic studies of C-X bond activation at transition-metal centers. In: Reedijik J, Poeppelmeier K (eds) Comprehensive inorganic chemistry II, vol 9. Elsevier, Amsterdam, pp 635–694
Svensson M, Humbel S, Froese RJD, Matsubara T, Sieber S, Morokuma K (1996) ONIOM: a multilayered integrated MO + MM method for geometry optimizations and single point energy predictions. A test for Diels-Alder reactions and Pt(P(tBu)3)2 + H2 oxidative addition. J Phys Chem 100:19357–19363
Bo C, Maseras F (2008) QM/MM methods in inorganic chemistry. Dalton Trans 2911–2919
Ahlquist MSG, Norrby PO (2011) Dispersion and back-donation gives tetracoordinate [Pd(PPh3)4]. Angew Chem Int Ed 50:11794–11797
Minenkov Y, Occhipinti G, Jensen VR (2009) Metal-phosphine bond strengths of the transition metals: a challenge for DFT. J Phys Chem A 113:11833–11844
Ryde U, Mata RA, Grimme S (2011) Does DFT-D estimate accurate energies for the binding of ligands to metal complexes? Dalton Trans 40:11176–11183
Sieffert N, Bühl M (2009) Noncovalent interactions in a transition-metal triphenylphosphine complex: a density functional case study. Inorg Chem 48:4622–4624
Zhao Y, Truhlar DG (2007) Attractive noncovalent interactions in the mechanism of Grubbs second-generation Ru catalysts for olefin metathesis. Org Lett 9:1967–1970
McMullin CL, Jover J, Harvey JN, Fey N (2010) Accurate modelling of Pd(0) + PhX oxidative addition kinetics. Dalton Trans 39:10833–10836
Miloserdov FM, McMullin CL, Belmonte MM, Benet-Buchholz J, Bakhmutov VI, Macgregor SA, Grushin VV (2014) The challenge of palladium-catalyzed aromatic azidocarbonylation: from mechanistic and catalyst deactivation studies to a highly efficient process. Organometallics 33:736–752
Häller LJL, Page MJ, Erhardt S, Macgregor SA, Mahon MF, Naser MA, Velez A, Whittlesey MK (2010) Experimental and computational investigation of C-N bond activation in ruthenium N-heterocyclic carbene complexes. J Am Chem Soc 132:18408–18416
Miloserdov FM, McKay D, Muñoz BK, Samouei H, Macgregor SA, Grushin VV (2015) Exceedingly facile Ph-X activation (X = F, Cl, Br, I) with Ru(II): arresting kinetics, autocatalysis, and mechanisms. Angew Chem Int Ed 6:8466–8470
Author information
Authors and Affiliations
Corresponding authors
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2015 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Perrin, L., Carr, K.J.T., McKay, D., McMullin, C.L., Macgregor, S.A., Eisenstein, O. (2015). Modelling and Rationalizing Organometallic Chemistry with Computation: Where Are We?. In: Macgregor, S., Eisenstein, O. (eds) Computational Studies in Organometallic Chemistry. Structure and Bonding, vol 167. Springer, Cham. https://doi.org/10.1007/430_2015_176
Download citation
DOI: https://doi.org/10.1007/430_2015_176
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-31636-9
Online ISBN: 978-3-319-31638-3
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)