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Journal of Organometallic Chemistry
Elsevier Sequoia S. A.
Journal of Organometallic Chemistry

Elsevier Sequoia S. A.

0022-328X

Journal of Organometallic Chemistry/Journal Journal of Organometallic ChemistrySCICCRAHCIEI
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    Computational investigation of the effect of alkoxy carbon substitution on the mechanism of carbonyl group reduction by 1-hydridosilatranes

    Pixler, Alexander S.DeLio, Ashley M.Varjosaari, Sami E.Skrypai, Vladislav...
    8页
    查看更多>>摘要：We undertook computational investigations to determine the effects of the electronic nature of the cage atoms on the energetics of the reduction of acetone by 1-hydridosilatranes. QTAIM analyses of the parent 1-hydridosilatrane 1H(6) and hexasubstituted silatranes 1Me(6) and 1F(6) showed that the change in charge induced by the donor/acceptor properties of the substituents remained almost entirely localized on the alkoxy carbon; the hydridic nature of the silicon-bound hydrogen as gauged by the charge remained essentially unchanged. This shows resilience to the electronic effects of the substituents at this position. The energetics of acetone reduction to 2-propanol were mapped out for all three cases. Calculations showed favorable Gibbs free energies for each reduction, with considerable exergonicities and modest barriers. Reductions using 1H(6) and 1Me(6) follow hydride transfer mechanisms without involvement of carbonyl oxygen that lead to an ion/neutral pair, while reduction using 1F(6) seems to involve a concerted sigma-metathesis-like mechanism that leads directly to a dialkoxysilatrane. (C) 2021 Elsevier B.V. All rights reserved.
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    Mechanistic insight into the [2+2+2] cycloadditions between 1,6-diyne and benzoquinone catalyzed by rhodium complex: A theoretical study

    Yun, XiaoYu, ZhangyuLiu, Tao
    5页
    查看更多>>摘要：The coupling reaction mechanism of 1,6-diyne with benzoquinone catalyzed by rhodium complex was studied by density functional theory (DFT) calculations. The [2 + 2 + 2] cycloaddition reaction include four main steps: oxidative cyclization, olefin insertion, a-bond metathesis, and H-transfer, respectively, which would lead to the major product naphthoquinone. The olefin insertion is the chemoselectivitydetermining step and the electronic effect could account for the observed chemoselectivity. The effect of different substituents of benzoquinone on the yield was also clarified through our calculations. (C) 2021 Elsevier B.V. All rights reserved.
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    • NSTL
    • Elsevier

    Effect of incorporation of silole and phosphole heterocycles into photoswitchable diarylethenes

    Verchozina, Yulia A.Lvov, Andrey G.
    13页
    查看更多>>摘要：A reversible interconversion of diarylethenes between two isomers became a powerful means for the development of new materials with a photoswitching function. The versatility of this phenomenon allows a wide variety of heterocyclic systems with advanced properties to be applied. In this mini-review, we analyzed the effect of incorporation of silole and phosphole heterocycles into the diarylethene framework, in particular, its effect on absorbance, quantum yields and thermal stability. The elusive aromaticity and high photostability of silole and phosphole derivatives allowed new highly efficient photoswitches to be obtained. Moreover, the phosphorous atom of the latter displayed a unique ability to undergo chemical modifications that was used for fine-tuning of molecules and development of functional photoswitches. These results clearly demonstrated that incorporation of more exotic moieties into diarylethene remains a promising way to advanced molecules and materials. (C) 2021 Elsevier B.V. All rights reserved.
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    • NSTL
    • Elsevier

    Regioselectivity in metalloradical catalyzed C-H bond activation: A theoretical study

    Das, Gourab KantiMukherjee, AnirbanSingh, RiteshMane, Kishor D....
    4页
    查看更多>>摘要：Pure quantum mechanical calculations were performed to find out the origin of regioselectivity under the metalloradical catalysis (MRC) by Co(II)-porphyrin, which showed regioselectivity is the inherent property of the aminyl radical generated from the sulfamoyl azide substrate. Different conformational analysis for the transition state from alpha-Co-III-aminyl radical to zeta-Co-III-alkyl radical formation have been studied to find out the most stable conformation for the preferable selectivity. The outcome of our study completely agrees with the reported experimental results. (C) 2021 Elsevier B.V. All rights reserved.
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    • NSTL
    • Elsevier

    Inkable CF3-functionalized benzothiazole/benzimidazole-Ir(III) complexes for efficient bilayer-inkjet-printed OLEDs

    Liao, Hao-SenHu, Yong-XuXia, XinXie, Dong-Dong...
    8页
    查看更多>>摘要：The inkjet-printed organic light-emitting diodes (OLEDs) are gradually gaining popularity due to their low cost, free vacuum environment, patterning, and large-area display capability, but inkable phosphors are yet less reported. In order to develop inkable phosphorescent luminescent material, the introduction of the strong electron-withdrawing CF3 in the C<^>N ligand of iridium(III) [Ir(III)] complexes is a wise choice. Herein, a serials of phosphorescent Ir(III) complexes consisting of 2-phenybenzothiazole/1,2-diphenylbenzimidazole with the introduction of CF3 group at ortho (o)/meta (m)/para (p) position of the phenyl ring abbreviated as (obt)(2)Ir(acac), (mbt)(2)Ir(acac), (pbt)(2)Ir(acac), (obm)(2)Ir(acac), (mbm)(2)Ir(acac), (Pbm)(2)Ir(acac), respectively, were designed and synthesized. The substituent effect and position effect of CF3 group based on the Ir(III) complexes were investigated in all aspects. The bilayer-inkjet-printed OLEDs with those phosphors were studied and showed promising electroluminescent performances. Among them, the OLEDs with (obt)(2)Ir(acac)/(obm)(2)Ir(acac) emitter exhibited the maximum external quantum efficiency of 3.7%/3.3%. In addition, the vacuum-deposited OLEDs with those Ir(III) phosphors as emitters were further investigated and demonstrated outstanding device performance. (C)2021 Elsevier B.V. All rights reserved.
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    • NSTL
    • Elsevier

    Protonation of Group 9 Metal (Co, Rh, Ir) Coordinated Bicyclo-[2.2.1]-hepta-2,5-diene and Bicyclo[2.2.2]octa-2,5-diene complexes: Facile Activation of Carbon-Carbon Bond in Bicyclo-[2.2.1]hepta-2,5-diene via M-H or M-H-C interactions

    Rahman, A. K. FazlurBennett, Martin A.
    10页
    查看更多>>摘要：The activation of C-C bond in coordinated M (eta(4) bicyclo [2.2.1]-hepta-diene) or 2,5-NBD via protonation for 3d,4d and 5d transition metals have been examined. Monoprotonation of the diolefin complexes [M(eta(C5R5)-C-5)(eta(4)- NBD] (R = H, CH3) M = Co, Rh,with CF3COOH or CF3SO3 H forms transient agostic metal hydrides (M-H-C) at -80 degrees C. Similar reaction with HPF6 (60% aq), the Ir analogues give terminal hydrides [IrH(eta(5)-C5Me4R)(eta(4) -2,5-NBD)]+PF6 (R=Me, or Et) as isolable solids at room temperature. All these hydride complexes coordinated to NBD subsequently undergo ligand migration to give stable eta(2)-vinyl eta(3) cyclopentenyl cations [M(eta(C5R5)-C-5) (C7H9)] -, (M=Co Rh, Ir). Protonation of the cobalt and rhodium co-ordinated bicyclo-[2.2.2]-octa 2,5- diene gives unstable M-H-C ground state structures at -80 degrees C, which decompose upon warming to room temp. Protonation reactions of the 2,5-BCOD complexes of Ir also give terminal hydrides [IrH(eta(5)-C5Me5)(eta(4)-2,5-BCOD)]+PF6 as (solids). Thermolysis of [IrH(eta(5)-C5Me5)(eta(4)-2,5-BCOD)]+PF6 did not give the expected, isomerized or C-C bond activated product, probably because 2,5-BCOD is less strained than 2,5-NBD. Coupling constant [J(CH)] and stretching frequency [v M-H] data indicate the electron density donation from the methyl groups in the Cp ring favors agostic structures. The C-C bond activation in the coordinated norbornadiene, via hydride migration is slower for the terminal hydride, M-H (M= Ir) compared to agostic hydrides for (M=Co, Rh) compounds. The vinyl cyclopentenyl cations of Rh,Ir undergo further isomerization in CF3COOH to give corresponding eta(6)-toluene cations [M(eta(5)-C5R5)(eta(6)-C6H5CH3)(+). At 50 degrees C in vacuo the salt [(eta(5)-C5Me5)Ir(H)(eta(4)nbd]+PF6 forms a neutral tetramethylfulvenyliridium (1) complex eta(C5Me4)-C-5=CH2)Ir(eta(NBD)-N-4) by C-H activation of a methyl group in the C5Me5 ring. (C) 2021 Elsevier B.V. All rights reserved.
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    • NSTL
    • Elsevier

    Silatrane-sulfonamide hybrids: Synthesis, characterization, and evaluation of biological activity

    Ushakov, Igor A.Oborina, Elizaveta N.Vashchenko, Alexander V.Adamovich, Sergey N....
    10页
    查看更多>>摘要：A series of novel sulfonamide-bridged silatranes 3,4,6,7 has been synthesized by the reaction of N,N-dichloroarylsulfonamides la-d with 1-vinylsilatrane 2 and 1-allylsilatrane 5. The structure of the silatrane-sulfonamide hybrids is characterized by elemental analysis, FT-IR, NMR (H-1, C-13, Si-29 and N-15) spectroscopy, high-resolution mass spectrometry, and X-ray diffraction analysis. The resulting hybrids 4ad and 7a-d have been investigated by computational screening via ADMET and PASS. These compounds exhibit drug-like features, bioavailability and may have high enzyme-inhibitory activity. The screening (in vitro) of hybrids 4a,b,d and 7a,b for antimicrobial activities against pathogenic bacterial strains shows that these compounds possess antibacterial properties. (C) 2021 Elsevier B.V. All rights reserved.
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    • NSTL
    • Elsevier

    Green and chemo selective amine methylation using methanol by an organometallic ruthenium complex

    Dindar, SaraKharat, Ali NematiAbbasi, Alireza
    5页
    查看更多>>摘要：Herein a green and convenient catalytic N-methylation of aniline and n-hexylamine using methanol as a dual methylation agent and solvent has been investigated. A new ruthenium carbonyl complex was synthesized and applied as a homogeneous catalyst in methylation reaction. The solid-state structure of the complex was determined by X-ray crystallographic analysis which indicate xantphos ligand bonded to ruthenium (II) as a tridentate pincer ligand by two P donor and one O atom. The catalytic system showed excellent conversion and selectivity toward N-methylaniline, and N,N-hexyldimethylamine at 140 degrees C. (c) 2021 Elsevier B.V. All rights reserved.
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    • NSTL
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    Catalytic N-diphosphonomethylation of amino alkanols and bisamino alkanes using tris(trimethylsilyl) phosphite as a convenient synthon

    Prishchenko, Andrey A.Alekseyev, Roman S.Novikova, Olga P.Livantsov, Mikhail, V...
    4页
    查看更多>>摘要：The new mono- and bis(aminomethylenediphosphonic) acids are synthesized for the first time via unique reaction of tris(trimethylsilyl) phosphite and various N-formyl amino alkanols or bis(N-formyl amino) alkanes at the presence of effective catalyst - trimethylsilyl triflate under mild conditions. The further treatment of initially formed trimethylsilyl intermediates with the methanol excess resulted in the crystalline mono- and bis(aminomethylenediphosphonic) acids in high yields. The catalytic scheme of target substances formation is proposed and discussed in detail. The structures of target acids were confirmed by the H-1, C-13, P-31 NMR spectra and high resolution mass spectra (HRMS). The resulting compounds are of great interest as perspective bioactive substances with versatile properties and effective polydentate ligands. (C) 2021 Elsevier B.V. All rights reserved.
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    Synthesis, characterization and electrochemical behavior of new bis(fluoroalkyl) ferrocenylphosphonates and their tin tetrachloride complexes

    Mechi, HanenSanhoury, M. A. K.Laribi, F.Manoury, E....
    9页
    查看更多>>摘要：The synthesis of fluoroalkyl and non-fluorinated long chain alkyl ferrocenylphosphonates of the type FcP(O)(OR)(2) (Fc: ferrocenyl; R = CH2CF3 (1), CH2C2F5 (2), Et (3) n-Hex (4), n-Hep (5) and n-Oct (6)) from reaction of ferrocene with corresponding phosphorochloridates is reported. The ferrocenyl phosphonates 1-4 were used as ligands, which reacted with tin(IV) chloride to produce the new complexes [SnCl4(1)(2)] (7), [SnCl4(2)(2)] (8), [SnCl4(3)(2)] (9) and [SnCl4(4)(2)] (10). All these ferrocenylphosphonate derivatives were characterized with multinuclear (H-1, C-13, F-19, P-31 and Sn-119) NMR, IR and UV-visible spectroscopic techniques. The electrochemical behavior of these compounds was investigated using cyclic voltammetry (CV); the results show that fluoroalkyl groups render the reverse one-electron transfer oxidation reaction more difficult (Delta E-1/2 = 310-330 mV) as compared to non-fluorinated alkyl groups (Delta E-1/2 = 215-261 mV). Preliminary results from CV measurements on the viability of ferrocenyl-containing tin(IV) complexes 7-10 as sensitizers for TiO2-based dye sensitized solar cells are also described. (C) 2021 Elsevier B.V. All rights reserved.
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    • NSTL
    • Elsevier