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  • 1.
    Ahlquist, Mårten
    et al.
    Scripps Research Insititute.
    Fokin, Valery V.
    Enhanced reactivity of dinuclear Copper(I) acetylides in dipolar cycloadditions2007In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 26, no 18, p. 4389-4391Article in journal (Refereed)
    Abstract [en]

    Dinuclear alkynyl copper(I) complexes exhibit superior reactivity toward organic azides compared to their monomeric analogues. DFT studies indicate that the second copper center facilitates the formation of the cupracycle in the rate-determining step and stabilizes the metallacycle intermediate itself. These findings support the experimentally determined rate law and shed light on the origin of high reactivity of the in situ generated copper acetylides.

  • 2.
    Ahlquist, Mårten
    et al.
    Technical University of Denmark.
    Fristrup, P
    Tanner, David
    Technical University of Denmark.
    Norrby, Per-Ola
    Technical Univeristy of Denmark.
    Theoretical evidence for low-ligated palladium(0): [Pd-L] as the active species in oxidative addition reactions2006In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 25, no 8, p. 2066-2073Article in journal (Refereed)
    Abstract [en]

    The oxidative addition of PhI to Pd-O has been studied by DFT with a continuum representation of the solvent. It is shown that the preferred number of ligands on palladium is lower than would be expected from "conventional wisdom" and the 18-electron rule. The most favored oxidative addition is obtained when Pd is coordinated by only the aryl iodide and one additional ligand in a linear arrangement. The calculations indicate that p-orbitals on the central metal are not involved in bonding in any of the complexes described herein, in good agreement with classic ligand field theory and also with a recent bonding analysis by Weinhold and Landis, but in apparent violation of the 18-electron rule.

  • 3.
    Ahlquist, Mårten
    et al.
    Technical University of Denmark.
    Kozuch, S
    Shaik, S
    Tanner, David
    Technical University of Denmark.
    Norrby, Per-Ola
    Technical Univeristy of Denmark.
    On the performance of continuum solvation models for the solvation energy of small anions2006In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 25, no 1, p. 45-47Article in journal (Refereed)
    Abstract [en]

    The determination of continuum solvation models for the solvation energy of anions, was described. To investigate the reliability of the solvent model, a few explicit THF molecules were incorporated. A set of anions was chosen for which the experimental free energiesof solvation were available for both H 2O and DMSO solutions. A major difference between the water model and the DMSO model is that the latter systematically overestimates the free energy of solvation. The full water model in Jaguar v 4.2, including also nonelectrostatic terms, gives good correlation with experimental values for energy of solvation.

  • 4.
    Ahlquist, Mårten
    et al.
    Technical University of Denmark.
    Norrby, Per-Ola
    Göteborg University.
    Oxidative addition of aryl chlorides to monoligated palladium(0): A DFT-SCRF study2007In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 26, no 3, p. 550-553Article in journal (Refereed)
    Abstract [en]

    Oxidative addition of aryl chlorides to palladium has been investigated by hybrid density functional theory methods (B3LYP), including a continuum model describing the solvent implicitly. A series of para-substituted aryl chlorides were studied to see the influence of electronic effects on the reaction. It was found that the experimentally observed higher reactivity of the more electron deficient aryl chlorides is due to their ability to accept back-donation from Pd-0 and form reasonably strong pre-reactive complexes. This effect is less pronounced in the transition state; when it is measured from the pre-reactive complex, the barrier to oxidative addition is actually higher for the electron-deficient aryl chlorides, but the overall reaction barrier is still lower than for the electron-rich aryl chlorides.

  • 5. Cheng, Mu-Jeng
    et al.
    Nielsen, Robert J.
    Ahlquist, Mårten
    KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
    Goddard, William A., III
    Carbon-Oxygen Bond Forming Mechanisms in Rhenium Oxo-Alkyl Complexes2010In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 29, no 9, p. 2026-2033Article in journal (Refereed)
    Abstract [en]

    Three C X bond formation mechanisms observed in the oxidation of (HBpz(3))ReO(R)(OTf) [HBpz(3) = hydrotris(1-pyrazolypborate; R = Me, Et, and iPr; OTf = OSO(2)CF(3)] by dimethyl sulfoxide (DMSO) were investigated using quantum mechanics (M06//B3LYP DFT) combined with solvation (using the PBF Poisson Boltzmann polarizable continuum solvent model). For R = Et we find the alkyl group is activated through alpha-hydrogen abstraction by external base OTf(-) with a free energy barrier of only 12.0 kcal/mol, leading to formation of acetaldehyde. Alternatively, ethyl migration across the M=O bond (leading to the formation of acetaldehyde and ethanol) poses a free energy barrier of 22.1 kcal/mol, and the previously proposed alpha-hydrogen transfer to oxo (a 2+2 forbidden reaction) poses a barrier of 44.9 kcal/mol. The rate-determining step to formation of the final product acetaldehyde is an oxygen atom transfer from DMSO to the ethylidene, with a free energy barrier of 15.3 kcal/mol. When R = iPr, the alkyl 1,2-migration pathway becomes the more favorable pathway (both kinetically and thermodynamically), with a free energy barrier (Delta G(double dagger) = 11.8 kcal/mol) lower than alpha-hydrogen abstraction by OTf(-) (Delta G(double dagger) = 13.5 kcal/mol). This suggests the feasibility of utilizing this type of migration to functionalize M-R to M-OR. We also considered the nucleophilic attack of water and ammonia on the Re-ethylidene alpha-carbon as a means of recovering two-electron-oxidized products from an alkane oxidation. Nucleophilic attack (with internal deprotonation of the nucleophile) is exothermic. However, the subsequent protonolysis of the Re alkyl bond (to liberate an alcohol or amine) poses a barrier of 37.0 or 42.4 kcal/mol, respectively. Where comparisons are possible, calculated free energies agree very well with experimental measurements.

  • 6. Haeffner, F.
    et al.
    Brinck, Tore
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.
    How does methyllithium invert? A density functional study2001In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 20, no 24, p. 5134-5138Article in journal (Refereed)
    Abstract [en]

    Quantum chemical studies (B3LYP) of the inversion of methyllithium in both tetrameric and dimeric aggregates have been carried out. Results show that inversion occurs either via dissociation of the tetramer into the dimers, passage of a four-membered-ring transition state, and association of the dimers to form the inverted tetramer, or via a nonconcerted route involving an eight-membered-ring transition state. The activation energies of these two mechanisms are similar. However, the dissociative mechanism is ruled out by NMR experiments.

  • 7. Johnson, Magnus T.
    et al.
    Johansson, Roger
    Kondrashov, Mikhail V.
    Steyl, Gideon
    Ahlquist, Mårten S. G.
    KTH, School of Biotechnology (BIO), Theoretical Chemistry.
    Roodt, Andreas
    Wendt, Ola F.
    Mechanisms of the CO2 Insertion into (PCP) Palladium Allyl and Methyl sigma-Bonds. A Kinetic and Computational Study2010In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 29, no 16, p. 3521-3529Article in journal (Refereed)
    Abstract [en]

    The reaction of the sigma-bonded (PCP)Pd-Me complex (PCP = 2,6-bis[(di-tert-butylphosphino)methyl]phenyl) with CO2 is first-order in palladium and first-order in CO, with a rate constant k(s) = 8.9 +/- 0.8 M-1 s(-1) at 353 K. Activation parameters are Delta H double dagger = 73 7 kJ/mol and Delta S double dagger = 118 +/- 19 J/K mol. Based on this and theoretical calculations we propose an S(E)2 mechanism where the coordinated methyl group attacks a completely noncoordinated carbon dioxide molecule in a bimolecular reaction. The PCPPd-crotyl complex was synthesized in an 65:35 E:Z mixture, and it was shown to react with CO, to give the complex PCPPd-O(CO)CH(CH3)CHCH2 as a single isomer, where the former gamma-carbon has been carboxylated. Theoretical calculations again suggest an S(E)2 mechanism with a noncoordinated carbon dioxide reacting with the terminal carbon on the allyl group, forming an eta(2)-bonded olefin complex as an intermediate. The rearrangement of this intermediate to the O-bonded product is concluded to be rate determining. The crystal structure of PCPPd-O(CO)C(CH3)(2)CHCH2 is reported and as well as the solubility of carbon dioxide in benzene-d(6) at different pressures and temperatures.

  • 8. Osadchuk, Irina
    et al.
    Tamm, Toomas
    Ahlquist, Mårten S. G.
    KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
    Theoretical Investigation of a Parallel Catalytic Cycle in CO2 Hydrogenation by (PNP)IrH32015In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 34, no 20, p. 4932-4940Article in journal (Refereed)
    Abstract [en]

    The (PNP)IrH3 (2,6-bis(diisopropylphosp-hinomethyl)pyridine iridium trihydride) complex by Nozaki is a highly active and selective catalyst for CO2 hydrogenation to formic acid in aqueous KOH. Previous theoretical investigations found that regeneration of the catalyst is the rate-determining step in this reaction. In the current article we present results from a computational study using density func- theory in order to consider the possibility of sequential insertion of two CO2 molecules in two Ir-H bonds before the reaction with hydrogen. We found that insertion of a second CO2 molecule is indeed possible; moreover, this sequential insertion allows formation of a more electrophilic iridium mono-hydride intermediate, and thereby the process of H-2 cleavage is facilitated. In addition, we considered the influence of ligands coplanar with the PNP ligand on the energy of CO2 insertion into the (PNP)IrH2X complex and found that sigma- and pi-donating ligands promote the reaction.

  • 9. Polukeev, Alexey V.
    et al.
    Marcos, Rocio
    KTH, School of Biotechnology (BIO).
    Ahlquist, Mårten S. G.
    KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
    Wendt, Ola F.
    Iridium Hydride Complexes with Cyclohexyl-Based Pincer Ligands: Fluxionality and Deuterium Exchange2016In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 35, no 16, p. 2600-2608Article in journal (Refereed)
    Abstract [en]

    Two hydride compounds with aliphatic pincer ligands, (PCyP)IrH2 (PCyP = {cis-1,3-bis[(di-tert-butylphosphino)methyl]cyclohexane}(-) (1) and (PCyP)IrH4 (2), have been studied, with emphasis on features where such systems differ from arene-based analogues. Both compounds reveal relatively rapid exchange between alpha-C-H and Ir-H, which can occur via formation of carbene or through demetalation, with nearly equal barriers. This observation is confirmed by deuterium incorporation into the alpha-C-H position. Complex 1 can reversibly add an N-2 molecule, which competes with the alpha-agostic bond for a coordination site at iridium. The hydrogen binding mode in tetrahydride 2 is discussed on the basis of NMR and IR spectra, as well as DFT calculations. While the interpretation of the data is somewhat ambiguous, the best model seems to be a tetrahydride with minor contribution from a dihydrido-dihydrogen complex. In addition, the catalytic activity of 1 in deuterium exchange using benzene-d(6) as a deuterium source is presented.

  • 10.
    Privalov, Timofei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Linde, C.
    Zetterberg, K.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Theoretical studies of the mechanism of aerobic alcohol oxidation with palladium catalyst systems2005In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 24, no 5, p. 885-893Article in journal (Refereed)
    Abstract [en]

    Density functional theory (DFT) was applied to a comprehensive mechanistic study of the Pd(II)-catalyzed oxidation of alcohols by molecular oxygen. Both parts of the catalytic cycle, i.e., the oxidative dehydrogenation of the substrate and the regeneration of the catalyst by the co-oxidant, molecular oxygen, were studied. The catalytic cycle under consideration consists of intramolecular deprotonation, beta-hydride elimination, and migratory insertion steps, and it is relevant for a wide class of catalytic systems. In particular, a Pd(II) cyclometalated system was addressed and qualitatively compared with the Uemura system (Pd(OAc)(2)/pyridine) and with the Pd-carbene system. Geometries of the intermediate complexes and relative Gibbs free energies were identified along the proposed reaction path with the help of computational methods. The transition state for the beta-hydride elimination, which is the highest point on the energy profile of the catalytic cycle, was identified.

  • 11.
    Privalov, Timofei
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Samec, Joseph S. M.
    Backvall, Jan- E.
    DFT study of an inner-sphere mechanism in the hydrogen transfer from a hydroxycyclopentadienyl ruthenium hydride to imines2007In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 26, no 11, p. 2840-2848Article in journal (Refereed)
    Abstract [en]

    A combination of the DFT method with the computational description of environmental effects by solvent was applied to a theoretical study of the hydrogen transfer to imines by [2,3,4,5-Ph-4(eta(5)-C4COH)Ru(CO)(2)H] (2) within a molecular model that closely mimics the authentic reaction conditions. A consistent polarizable continuum solvent model (PCM) was instrumental and necessary in achieving stability of the computational model. Environmental effects by solvent were also considered in an extended model with an addition of explicit solvent molecules within the PCM. The study elucidates an inner-sphere mechanism in detail. Intermediate complexes and transition states are characterized. Three distinct energy barriers along the reaction coordinate are predicted when solvent effects are taken into account. The imine coordinates to ruthenium via ring slippage with an energy barrier of about 15 kcal/mol. Close in energy (12 kcal/mol) is the transition state of the hydride transfer, which gives an (eta(2)-cyclopentadienone)ruthenium amine intermediate. The presence of Ph groups on the Cp ring facilitates the ring slippage that occurs on imine coordination. This eta(2)-intermediate finally rearranges to the corresponding (eta(4)-cyclopentadienone)ruthenium amine complex via a transition state at 9 kcal/mol. The stable ruthenium amine complex was verified against an X-ray structure of the corresponding complex. Inclusion of the solvent (by PCM or explicit molecules) was required to stabilize low-hapticity intermediates and transition state structures.

  • 12. Ryabov, A. D.
    et al.
    Panyashkina, I. M.
    Polyakov, V. A.
    Fischer, Andreas
    KTH, Superseded Departments, Chemistry.
    Access to central carbon chirality through cycloplatination of 1-(2-pyridinylthio)propanone by cis- PtCl2(S-SOMe(p-tolyl)) . The crystal structure of (SsSc)- Pt{py{SCHC(O)Me}-2}Cl(SOMe(p-tolyl))2002In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 21, no 8, p. 1633-1636Article in journal (Refereed)
    Abstract [en]

    Cycloplatination of the prochiral sp(3)C-H bond of 1-(2-pyridinylthio)propanone (py(SCH2C(O)Me)(-2), 1a) by cis-[PtCl2(SOMe2)] in dry ethanol affords [Pt(py(SCHC(O)Me)-2)Cl(SOMe2)] (3a) in 77% isolated yield without any side product. The same reaction using the chiral complex cis-[PtCl2(S-SOMe(p-tolyl))] (the absolute configuration of sulfur is indicated for the coordinated ligand) leads to two cycloplatinated diastereoisomers, 4a (SsRc) and 4b (SsSc), in 12.9 and 33.7% yield, respectively (de 44.6%). Their absolute configuration was deduced from the analysis of the H-1 NMR spectra and confirmed by an X-ray structural investigation of 4b. Diastereomer 4b was shown to react with PPh3 to give the enantiomer [Pt(py(SCHC(O)Me)-2)Cl(PPh3)] with the central carbon chirality only. Rather surprisingly, attempted cycloplatination Of py(SCH2C(O)Ph)-2 (1b) by cis-[PtCl2(SOMe2)] affords the cycloplatinated complex [Pt(pyf(SCHC(O)Ph)-2)Cl(SOMe2)] (3b) in a miserable yield.

  • 13. Stokes, F.A.
    et al.
    Less, R.J.
    Haywood, J.
    Melen, Rebecca L.
    Thompson, R.L.
    Wheatley, A.E.
    Wright, D.S.
    Johansson, Adam Johannes
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry (closed 20110630).
    Kloo, Lars
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Structure and Bonding of the Manganese(II) Phosphide Complex (t-BuPH(2))(eta(5)-Cp)Mn{mu-(t-BuPH)}(2)Mn(Cp)(t-BuPH(2))2012In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 31, no 1, p. 23-26Article in journal (Refereed)
    Abstract [en]

    Rather than achieving bis-deprotonation of the phosphine, reaction of Cp2Mn (Cp = cyclopentadienyl) with t-BuPH2 at room temperature yields monodeprotonation of half of the available phosphine in the product (t-BuPH2)(η5-Cp)Mn{μ-(t-BuPH)}2Mn(Cp)(t-BuPH2) (1). This complex comprises a Mn(II) phosphide and is a dimer in the solid state, containing a Mn2P2 diamond core. Consistent with the observation of a relatively short intermetal distance of 2.8717(4) Å in 1, DFT analysis of the full structure points to a singlet ground state stabilized by a direct Mn–Mn single bond. This is in line with the diamagnetic character of 1 and an 18-electron count at Mn.

  • 14.
    Theveau, Laure
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Bellini, Rosalba
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Dydio, Pawel
    Szabo, Zoltan
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    van der Werf, Angela
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry. University of Amsterdam, Netherlands.
    Sander, Robin Afshin
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Reek, Joost N. H.
    Moberg, Christina
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    Cofactor-Controlled Chirality of Tropoisomeric Ligand2016In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 35, no 11, p. 1956-1963Article in journal (Refereed)
    Abstract [en]

    A new tropos ligand with an integrated anion receptor receptor site has been prepared. Chiral carboxylate and phosphate anions that bind in the anion receptor unit proved capable of stabilizing chiral conformations of the achiral flexible bidentate biaryl phosphite ligand, as shown by variable temperature H-1 and P-31 NMR spectroscopical studies of palladium(0) olefin complexes. Palladium allyl complexes of the supramolecular ligand-chiral cofactor assemblies catalyzed asymmetric allylic substitutions of rac-(E)-1,3-diphenyl-2-propenyl carbonate and rac-3-cyclohexenyl carbonate with malonate and benzylamine as nucleophiles to provide nonracemic products. Although moderate enantioselectivities were observed, (ee:s up to 66%), the results confirm the ability of the anionic guests to affect the conformation of the ligand.

  • 15.
    Wang, Ying
    et al.
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.
    Zhan, Shaoqi
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.
    Ahlquist, Mårten S. G.
    KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.
    Nucleophilic Attack by OH2 or OH-: A Detailed Investigation on pH Dependent Performance of a Ru Catalyst2019In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 38, no 6, p. 1264-1268Article in journal (Refereed)
    Abstract [en]

    The considerable rate enhancements along with the increase in pH values may be due to the direct involvement of hydroxide anion in attacking electrophilic [Ru-V(tda)(py)(2)O](+) (1; tda = [2,2':6',2 ''-terpyridine]-6,6 ''-dicarboxylate, py = pyridine). The enhanced reaction rate is well in agreement with the descending activation barriers in our calculation. The addition of four extra water molecules in the geometry optimization plays a key role in stabilizing hydroxide anion as well as building a reasonable hydrogen-bonding network, and three of these molecules are required to stabilize the OH as an anion instead of a radical.

  • 16.
    Westlund, Robert
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Vestberg, Robert
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Glimsdal, Eirik
    Lindgren, Mikael
    Lopes, Cesar
    Malmström, Eva E.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Synthesis and Characterization of a 3-Arm Star Platinum(II) Acetylide Chromophore Targeted for Optical Limiting ApplicationsIn: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041Article in journal (Other academic)
  • 17. Zierkiewicz, W.
    et al.
    Privalov, Timofei
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
    A theoretical study of the essential role of DMSO as a solvent/ligand in the Pd(OAc)(2)/DMSO catalyst system for aerobic oxidation2005In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 24, no 24, p. 6019-6028Article in journal (Refereed)
    Abstract [en]

    Dimethyl sulfoxide (DMSO) has unique properties as an aprotic, polar solvent. The oxygen atom in DMSO can interact with positive charges and thus stabilize metal cation. The sulfur atom, although somewhat positively charged, does not interact with negative charges effectively. Also, two methyl groups surround the sulfur atom and influence binding properties of DMSO. These features of DMSO are addressed in the present computational study of the Pd(AcO)(2)/DMSO-catalyzed aerobic oxidation system. Mechanistic and computational details are provided. The step-by-step Gibbs energy of reaction was calculated using the electronic energy at the B3LYP density functional level with thermal functions calculated at the same level of theory. The solvent was modeled using the polarized medium (PCM) with additional DMSO molecules in the second coordination sphere of the complexes studied. The overall reaction pathway was divided into several steps in accord with available experimental data. All steps, including the first deprotonation and the beta-hydride elimination transition states, were elucidated in good detail. Coordination and reorganization of DMSO in Pd(II)(AcO)(2)/DMSO and Pd(0)/(DMSO)(n) complexes has been studied to provide realistic data about coordination of DMSO with hard (O) versus soft (S) ligand donor atoms. The P-hydride elimination transition state was identified computationally to give an estimation of the activation energy of the alcohol oxidation reaction. Therefore, we suggest that the rate-determining step is related to the alcohol part of the reaction cycle.

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