Dmitry V. Gutsulyak

The University of Calgary, Calgary, Alberta, Canada

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Publications (13)91.6 Total impact

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    ABSTRACT: The (PCP)Ni-OH complexes 2R (R = iPr, tBu, Cy) are effective catalyst precursors for the selective hydration of nitriles to the corresponding amides under relatively mild conditions (80 ˚C) and low catalyst loadings (0.05-0.5%). Substrate scope includes aliphatic, vinylic and aromatic nitriles, but substrates with protic groups poison the catalyst abruptly. The catalysts are effective because the electron rich nature of the PCP ligands and their steric bulk renders the hydroxo group labile.
    Dalton Transactions 01/2015; 44(27). DOI:10.1039/C4DT03902E · 4.20 Impact Factor
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    ABSTRACT: The syntheses and structures of new bis-N-phenyl-4-cyano-β-diketiminate (1), bis-N-phenyl-2-cyano-β-diketiminate (2), N-phenyl-4-cyano-N-phenyl-2-cyano-β-diketiminate (3), N-phenyl-4-cyano-N-2,6-diisopropylphenyl-β-diketiminate (4), N-phenyl-2-cyano-N-2,6-diisopropylphenyl-β-diketiminate (5), and methallyl nickel complexes [L1Ni(η3-methallyl)] (6), [L2Ni(η3-methallyl)] (7), [L4Ni(η3-methallyl)] (8), and [L5Ni(η3-methallyl)] (9) from the reaction of deprotonated ligands 1/2, 4/5, and methallylnickel chloride dimer are reported. Subsequent reactions of complexes 6–9 with tris(pentafluorophenyl)boron give rise to new adducts [L1Ni(η3-methallyl)]·2B(C6F5)3 (10), [L2Ni(η3-methallyl)]·2B(C6F5)3 (11), [L4Ni(η3-methallyl)]·B(C6F5)3 (12), and [L5Ni(η3-methallyl)]·B(C6F5)3 (13), where B(C6F5)3 is coordinated to the cyano group. New compounds are characterized by NMR, IR, and mass spectrometry techniques, and crystal structures of most compounds are obtained and described. Complexes 6–9, adducts 10–13, and adducts 10–13 with 5 equiv of B(C6F5)3 have been investigated toward ethylene activation. Complexes 6–9 were inactive toward ethylene even at 60 °C, while adducts 10–13 showed reactivity toward ethylene; adding 5 equiv of B(C6F5)3 to adducts 10–13 leads to an increase in reactivity toward ethylene. Adducts 10 and 11 alone and with 5 equiv of B(C6F5)3 catalyze the oligomer formation, while adducts 12 and 13 by the same conditions catalyze the polyethylene formation. Adduct 13 activity is five times higher with respect to 12 at 50 °C and two times higher at 70 °C. The formation of branched moderate molecular weight PE by 12/B(C6F5)3 and 13/B(C6F5)3 is observed.
    Organometallics 11/2013; 32(24):7323–7333. DOI:10.1021/om400847b · 4.13 Impact Factor
  • Dmitry V Gutsulyak · Warren E Piers · Javier Borau-Garcia · Masood Parvez
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    ABSTRACT: Nickel complexes of a PCcarbeneP pincer ligand framework are described. Dehydrobromination of the precursor (PCsp(3)P)NiBr in the presence of a donor (PPh3 or NC(t)Bu) leads to the title complexes, which feature a rare nickel-carbene linkage as the pincer ligand anchor point. This strongly donating, nucleophilic carbene center engages in a variety of E-H bond activations (E = H, C, N, O), some of which are reversible. This represents a new mode of bond activation by ligand cooperativity in nickel pincer complexes.
    Journal of the American Chemical Society 08/2013; 135(32). DOI:10.1021/ja406742n · 12.11 Impact Factor
  • Sun-Hwa Lee · Dmitry V. Gutsulyak · Georgii I. Nikonov
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    ABSTRACT: The ruthenium complex [Cp(iPr3P)Ru(NCCH3)2]+ (1) catalyzes the regioselective hydrosilylation of pyridines to 1,4-dihydropyridines. Substitution in the 3- and 5-positions is tolerated, whereas pyridines with substituents in the 2-, 4-, and 6-positions are not reduced. Reduction of functionalized pyridines having keto and ester substituents results in a mixture of products. N-Silyl-1,4-dihydropyridine reacts with ketones and aldehydes to give products of N–Si addition across the C═O bond. Hydrosilylation of pyridine in acetone results quantitatively in the addition product PhMe2SiO–CMe2–NC5H6, which decomposes in hexane to give the parent dihydropyridine HNC5H6. The phenanthroline complex [Cp(phen)Ru(NCCH3)2]+ (10) catalyzes regioselective 1,4-reduction of phenanthroline by a 3–4-fold excess of silane/water or silane/alcohol mixtures. The Cp* analogue [Cp*(phen)Ru(NCCH3)2]+ (9) catalyzes 1,4-regioselective monohydrosilylation of phenanthroline, quinoline, acridine, and 1,3,5-triazine and the 1,2-reduction of isoquinoline. In contrast, 2-substituted phenanthroline, pyrazine, 2-ethylpyridine, 2,6-lutidine, 2,4-lutidine, and pyrimidine are not reduced under these conditions by either of the catalysts studied.
    Organometallics 06/2013; 32(16):4457–4464. DOI:10.1021/om400269q · 4.13 Impact Factor
  • Dmitry V. Gutsulyak · Andrew L. Gott · Warren E. Piers · Masood Parvez
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    ABSTRACT: Trifluoroborate-functionalized phosphine ligands react with a variety of nickel(II) precursors to cleanly yield a number of κ2(P,F)-bound nickel complexes, which were characterized crystallographically. In comparison to related palladium complexes, ancillary ligands in the nickel complexes were observed to be generally more weakly bound, and the trifluoroborate ligands were more easily displaced by coordinating solvents that did not cause a similar displacement in a related palladium system. Such weaker ligand coordination resulted in a much faster dimerization of ethylene. Experiments conducted under constant ethylene pressure saw the suppression of the isomerization of 1-butene observed in related palladium complexes; higher oligomers were also generated under such conditions.
    Organometallics 05/2013; 32(11):3363–3370. DOI:10.1021/om400288u · 4.13 Impact Factor
  • Dmitry V. Gutsulyak · Georgii I. Nikonov
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    ABSTRACT: AbstractA variety of aromatic and alkyl acid chlorides can be selectively converted into aldehydes using dimethylphenyl silane (HSiMe2Ph) as the reducing reagent in the presence of the cationic ruthenium catalyst {Cp[(i‐Pr)3P]Ru(NCMe)2}+ [PF6]−. The reactions proceed under very mild conditions and are tolerant to many functional groups.
    Advanced Synthesis & Catalysis 07/2012; 354(4). DOI:10.1002/adsc.201100693 · 5.66 Impact Factor
  • Dmitry V Gutsulyak · Art van der Est · Georgii I Nikonov
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    ABSTRACT: Nicht nur überraschend einfach, sondern zudem 1,4-regioselektiv und reversibel verläuft die Hydrosilylierung von Pyridinen mit [Cp(iPr3P)Ru(NCCH3)2]+ (Cp=Cyclopentadienyl) als Katalysator. Die Produkte können auf vielfältige Art weiter umgesetzt werden (siehe Schema). Der verwandte Komplex [CpRu(NCCH3)3]+ katalysiert die Reduktion von Phenanthrolin durch HSiMe2Ph/Wasser, bei der zwei H-Atome übertragen werden.
    Angewandte Chemie International Edition 02/2011; 50(6):1384-7. DOI:10.1002/anie.201006135 · 11.26 Impact Factor
  • Dmitry V Gutsulyak · Georgii I Nikonov
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    ABSTRACT: Monohydrosilylation of nitriles (I) and (VI) proceeds smoothly in the presence of a cationic Ru complex to give N-silylimines under mild reaction conditions.
    Angewandte Chemie International Edition 10/2010; 49(41):7553-6. DOI:10.1002/anie.201003069 · 11.26 Impact Factor
  • Dmitry V Gutsulyak · Sergei F Vyboishchikov · Georgii I Nikonov
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    ABSTRACT: Hydrosilylation of carbonyls catalyzed by 2 goes via intermediate formation of cationic silane sigma-complexes 4 which undergo nucleophilic abstraction of the silylium cation studied by DFT calculations.
    Journal of the American Chemical Society 04/2010; 132(17):5950-1. DOI:10.1021/ja101583m · 12.11 Impact Factor
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    ABSTRACT: The Cp ring is found to exert a primarily electronic effect on the strength of Si−H interaction in silane σ-complexes Cp(Pri3P)RuCl(η2-HSiClR2). Complexation of chlorosilanes HSiClR2 is supported by an additional RuCl···SiCl interaction.
    Organometallics 05/2009; 28(9). DOI:10.1021/om801192b · 4.13 Impact Factor
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    ABSTRACT: This paper reports preparation of new silyl hydride complexes of ruthenium supported by the Cp/PR(3) ligand set. It is shown that the easiest and most general route to these complexes is provided by the thermal reaction of [RuCp(PR(3))(H)(3)] with hydrosilanes. Complexes [RuCp(PR(3))(H)(2)(SiMe(2)Cl)] exhibit Interligand Hypervalent Interactions (IHI) between the hydride and silyl ligands. Comparison of the X-ray structures of complexes [RuCp(PPr(i)(3))(H)(2)(SiMe(2)Cl)], [RuCp(PPhPr(i)(2))(H)(2)(SiMe(2)Cl)], and [RuCp(PPh(3))(H)(2)(SiMe(2)Cl)] shows that the IHI weakens with the decreasing electron-releasing ability of the phosphine. Comparison of the X-ray structure of [RuCp(PPh(3))(H)(2)(SiMe(2)Cl)] with the structure of the previously reported complex [RuCp*(PPh(3))(H)(2)(SiMe(2)Cl)] reveals that the lack of IHI in the latter compound is due to unfavourable steric interactions between the bulkier Cp* ring and the SiMe(2)Cl group.
    Dalton Transactions 01/2009; DOI:10.1039/b806447d · 4.20 Impact Factor
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    ABSTRACT: Reactions of a new borohydride complex 2 with hydrosilanes afford half-sandwich dihydride silyl complexes 3a-f. According to X-ray and DFT evidence complexes 3 have unprecedented double H...Si...H interligand interactions.
    Journal of the American Chemical Society 04/2008; 130(12):3732-3. DOI:10.1021/ja800983n · 12.11 Impact Factor
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    ABSTRACT: This paper reports facile preparation of half-sandwich trihydrido complexes of ruthenium based on the reactions of the readily available precursors [Cp(R3P)Ru(NCCH3)2][PF6] with LiAlH4. The target complexes were characterized by spectroscopic methods and X-ray structure analysis of Cp(PhPr2iP)RuH3.
    Journal of Organometallic Chemistry 10/2007; 692(22):5081-5085. DOI:10.1016/j.jorganchem.2007.07.024 · 2.17 Impact Factor