Hypervalent benzophenones
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Evgeniya P. Doronina, Valery F. Sidorkin, Elena F. Belogolova, Viatcheslav Jouikov Benzophenones (BPs) of the type 2-R-BP and 2,2′-R-BP, carrying silicon- or germanium-containing substituents R (R = EY2X; E = Si, Ge; Y = H, Me, F, Cl; X = H, F, Cl, OTf) at one or at two ortho-positions of the arene rings, were theoretically designed. Among 26 compounds considered, only 10 mono-substituted 2-R-BP and 5 bis-substituted 2,2′-R-BP (in hexane and DMSO solutions) belong to the first examples of hy...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Oxygen atom transfer to platinum(II): A 2-pyridyloxaziridine and a 2-pyridylnitrone as potential oxygen atom donors
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Nasser Nasser, Mahmood Azizpoor Fard, Paul D. Boyle, Richard J. Puddephatt The oxygen atom transfer reactions of 2-pyridyl-N-t-butyloxaziridine, pyox, with the dimethylplatinum(II) complex [Pt2Me4(μ-SMe2)2], 1, have been studied. In the presence of methanol or water, proton coupled oxygen atom transfer occurs, with displacement of dimethylsulfide ligands by the product ligand 2-pyridyl-N-t-butylmethanimine, pyim, to give initially the complexes [Pt(OH)(OR)Me2(pyim)], R = Me or H, respectively, which were slowly ...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Comparing the asymmetric dppf-type ligands with their semi-homologous counterparts
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Petr Vosáhlo, Ivana Císařová, Petr Štěpnička Two series of asymmetric ferrocene diphosphines, namely the dppf-type ligands R2PfcPPh2 (protected as BH3 adducts; fc = ferrocene-1,1′-diyl) and their singly-homologous counterparts R2PfcCH2PPh2 (both in free and BH3-protected form), with diverse PR2 groups (R = cyclohexyl, isopropyl and tert-butyl), were prepared and further converted into the respective phosphine selenides, R2P(Se)fcP(Se)Ph2 and R2P(Se)fcCH2P(Se)Ph2, which were ...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Syntheses, structures and reactivity of dinuclear organoruthenium-nickel complexes with N,N ′-bis(2-thiobenzylidene)-1,2-phenylenediaminato (tsalphen) ligand
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Ai-Quan Jia, Li-Hua Tang, Xian-Ping Dong, Zhifeng Xin, Qian-Feng Zhang Treatment of metalloligand [Ni(tsalphen)] (tsalphen = N,N′-bis(2-thiobenzylidene)-1,2-phenylenediaminato) with [(η 6-p-cymene)RuCl(μ-Cl)]2 or [CpRu(PPh3)2Cl] afforded cationic “Ni(μ-S)2Ru” bimetallic complexes [(η 6-p-cymene)Ru{Ni(tsalphen)}(MeCN)](OTf)2 (1) and [CpRu{Ni(tsalphen)}(PPh3)]2(NiCl4)⋅4MeOH (2), respectively, which are characterized by single-crystal X-ray diffraction, and their catalytic activity...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Transsilylation of O-trimethylsilyl derivatives of α-dimethylaminoketones by chloro(chloromethyl)dimethylsilane
Publication date: Available online 17 January 2018 Source:Journal of Organometallic Chemistry Author(s): Boris A. Gostevskii, Alexander I. Albanov, Alexander V. Vashchenko, Nataliya F. Lazareva Reaction of O-trimethylsilyl (O-TMS) derivatives of α-dimethylamino ketones with chloro(chloromethyl)dimethylsilane led to the formation of six-membered heterocyclic compounds with tetracoordinated silicon atom - 3,4-dihydro-2H-1,4,2-oxazasiline-4-ium chlorides. The exchange reactions of 2,2,4,4-tetramethyl-6-phenyl-3,4-dihydro-2H-1,4,2-oxazasilin-4-ium chloride were examined with Me3SiI and NaBPh4 and the corresponding iodid...
Source: Journal of Organometallic Chemistry - January 17, 2018 Category: Chemistry Source Type: research

From oxo to carbonyl and arene complexes; A journey through technetium chemistry
Publication date: Available online 17 January 2018 Source:Journal of Organometallic Chemistry Author(s): Roger Alberto A personal note in celebration of Professor Herrmann's 70th birthday, the author describes how the successful preparation of H3C99TcO3 and the still unsolved task of preparing [Cp*99TcO3] powered ultimately a plethora of organometallic 99Tc chemistry. Driven by the need for technetium carbonyl complexes, the red wire leads from [99TcCl3(CO)3]2- over the related [99mTc(OH2)3(CO)3]+ and [(L3)99TcO3]+ finally to [99Tc(arene)2]+ complexes. It is shown how, from the fundamental search for [Cp*99TcO3], useful m...
Source: Journal of Organometallic Chemistry - January 17, 2018 Category: Chemistry Source Type: research

Why is bis-indenylchromium a dimer? A DFT investigation
Publication date: Available online 13 January 2018 Source:Journal of Organometallic Chemistry Author(s): Bachir Zouchoune, Saber-Mustapha Zendaoui, Jean-Yves Saillard Unsubstituted bis-indenylchromium has been shown to be a dimer, Cr2(Ind)4, whereas the monomeric sandwich-type structure, Cr(Ind)2, has been only observed for substituted relatives. DFT calculations indicate that dimerization allows the building of a quadruple Cr-Cr bond whereas it can still participate in five formal 2-electron metal-ligand bonds. Despite of this apparently favorable situation with respect to dimer stability, the energetic balance in favor ...
Source: Journal of Organometallic Chemistry - January 13, 2018 Category: Chemistry Source Type: research

Amine adducts of (4-ClC6H4)3B3O3, Lewis acidity of triarylboroxines, and an XRD study on the related tetraphenylboroxinate(1-) salt, [C6H11NMe3][Ph4B3O3]
Publication date: Available online 11 January 2018 Source:Journal of Organometallic Chemistry Author(s): Michael A. Beckett, Simon J. Coles, Peter N. Horton, Charlotte L. Jones, Elizabeth V. Marshall, Thomas Perry The stoichiometric reactions of amines with tri(4-chlorophenyl)boroxine (CPB) led to the formation of adducts CPB.L {L = morpholine (1a), benzylamine (1b) cyclohexylamine (1c), 2-picoline (1d), 4-picoline (1e), piperidine (1f)} and (CPB)2 .(4,4′-trimethylenedipiperidine) (1g). Compounds 1a-1g have been characterized by NMR (11B, 1H, 13C), IR spectroscopy and powder-XRD. VT 1H NMR spectra on 1a and 1d-1...
Source: Journal of Organometallic Chemistry - January 12, 2018 Category: Chemistry Source Type: research

Polymer-anchored [Fe(III)Azo] complex: An efficient reusable catalyst for oxidative bromination and multi-components reaction for the synthesis of spiropiperidine derivatives
Publication date: Available online 11 January 2018 Source:Journal of Organometallic Chemistry Author(s): Resmin Khatun, Surajit Biswas, Swarbhanu Ghosh, Sk Manirul Islam A heterogeneous catalyst was prepared by attaching Fe(III) into organically modified chloromethylated polytstyrene and characterized by AAS, IR, PXRD, TG-DTA, UV–Vis, and SEM studies. In presence of H2O2 and KBr as bromine source, the catalyst showed remarkably high conversion with para-selectivity towards the oxidative bromination reaction in acetic acid medium. The catalyst was also very active and highly efficient for the production of spiropiper...
Source: Journal of Organometallic Chemistry - January 12, 2018 Category: Chemistry Source Type: research

Theoretical studies on copper-catalyzed arylation of nitrogen heterocycles from benzenediazonium acetate under ligand-free conditions
Publication date: Available online 10 January 2018 Source:Journal of Organometallic Chemistry Author(s): Khalil Ahmad, Chun-Ran Chang, Jun Li The density functional theory (DFT) method was used to investigate the mechanism of ligand-free copper-catalyzed arylation of nitrogen heterocycles from benzenediazonium acetate. Two possible mechanisms, single electron transfer and oxidative addition/reductive elimination reaction mechanism were investigated for two possible Cu(I) complexes in the reaction solution. Complex 1 has an acetate and a pyrazole ligand coordinated to Cu(I), and complex 2 has two pyrazole ligands coordinat...
Source: Journal of Organometallic Chemistry - January 11, 2018 Category: Chemistry Source Type: research

Assessing Ge-132 as an antioxidant in organic and water-containing media
Publication date: Available online 10 January 2018 Source:Journal of Organometallic Chemistry Author(s): Antonina A. Vishtorskaya, Evgeniya A. Saverina, Valery M. Pechennikov, Irina V. Krylova, Andrey V. Lalov, Mikhail A. Syroeshkin, Mikhail P. Egorov, Viatcheslav V. Jouikov The antioxidant activity of Ge-132 (2-carboxyethylgermanium sesquioxide, [(O0.5)3GeCH2CH2COOH] n ), a widely used organic germanium dietary supplement, was assessed by cyclic voltammetry and through its interaction with a stable radical 2,2,-diphenyl-1-picrylhydrazyl (DPPH) monitored by UV-Vis and EPR spectroscopy in water, CH3CN, DMF, MeOH, and their...
Source: Journal of Organometallic Chemistry - January 11, 2018 Category: Chemistry Source Type: research

DFT study of substituent effects in the hydroxylation of methane and toluene mediated by an ethylbenzene dehydrogenase active site model
Publication date: Available online 10 January 2018 Source:Journal of Organometallic Chemistry Author(s): J. Oscar C. Jimenez-Halla, Azadeh Nazemi, Thomas R. Cundari Density functional theory (DFT) was applied to mimic active species of ethylbenzene dehydrogenase (EBDH), a molybdoenzyme. Considering the impact of several aspects including transition metals, Brønsted-Lowry acid/base conjugate pairs, the trans effect, and supporting ligands upon the relevant activation barriers for methane and toluene led to conclusions that, on average, the transition states for methane activation/functionalization are roughly 13 k...
Source: Journal of Organometallic Chemistry - January 11, 2018 Category: Chemistry Source Type: research

Zinc and copper complexes of stilbene iminopyridine ligands with η2-Olefin binding mode
Publication date: Available online 9 January 2018 Source:Journal of Organometallic Chemistry Author(s): Awatef Ayadi, Mohamed-Ali Benmensour, Yohan Cheret, Abdou Boucekkine, Abdelkrim El-Ghayoury Two stilbene based iminopyridine ligands (L1-L2) synthesized by a condensation reaction between N,N-Dimethyl-4,4′-azodianiline and 2-pyridinecarboxaldehyde or 2,6-pyridinedicarboxaldehyde, with 73% and 65% yield, are described. The two ligands have been characterized by elemental analysis and spectroscopic techniques. The complexation of ligand L1 with ZnCl2 afforded neutral tetrahedral zinc(II) metal complex C1 formulated ...
Source: Journal of Organometallic Chemistry - January 10, 2018 Category: Chemistry Source Type: research

Xanthine based N-heterocyclic carbene (NHC) complexes
Publication date: Available online 9 January 2018 Source:Journal of Organometallic Chemistry Author(s): Hugo Valdés, Daniel Canseco-González, Juan Manuel German-Acacio, David Morales-Morales N-heterocyclic carbene (NHC) complexes derived from xanthines have attracted much attention. Xanthines comprise a wide range of compounds, among which the best known are caffeine, theophylline and theobromine. Xanthine-NHC complexes have been used as catalysts, antimicrobial, anticancer agents and for their photoluminescent properties. The easy functionalization of xanthines along with their biological activity makes the...
Source: Journal of Organometallic Chemistry - January 10, 2018 Category: Chemistry Source Type: research

Performance of chiral tetracarbonylmolybdenum pyrindanyl amine complexes in catalytic olefin epoxidation
Publication date: Available online 8 January 2018 Source:Journal of Organometallic Chemistry Author(s): Patrícia Neves, Lucie S. Nogueira, Anabela A. Valente, Martyn Pillinger, Isabel S. Gonçalves, Ivo E. Sampaio-Dias, Carlos A.D. Sousa, Fabio Rizzo-Aguiar, José E. Rodríguez-Borges Tetracarbonylmolybdenum(0) complexes of the type cis-[Mo(CO)4(L)] containing chiral 7-(1-pyrindanyl) amine ligands were prepared and found to be effective precatalysts for the epoxidation of achiral (cis-cyclooctene) and prochiral (DL-limonene and trans-β-methylstyrene) olefins at 55 °C. Epoxides were the ...
Source: Journal of Organometallic Chemistry - January 9, 2018 Category: Chemistry Source Type: research

Theoretical insight into the mechanisms of palladium-catalyzed intramolecular insertion of alkenes into the carbon-nitrogen bond of β-lactam
Publication date: Available online 6 January 2018 Source:Journal of Organometallic Chemistry Author(s): Jing Zhang, Benzhen Xu, Weirong Wu, Tao Liu By employing density functional theory (DFT), we investigate the mechanisms of Pd-catalyzed intramolecular alkene insertion with β-lactam. The catalytic cycle involves oxidative addition, alkene insertion, and reductive elimination. In reaction A, the rate-determining step is the alkene insertion. Compared with reaction A, the higher barriers for reactions B and C could be attributed to the weaker electron-donating ability of ligands and the strong steric repulsion betwee...
Source: Journal of Organometallic Chemistry - January 7, 2018 Category: Chemistry Source Type: research

Lutetium functionalities supported by a sterically encumbered β-diketiminate ligand
Publication date: Available online 6 January 2018 Source:Journal of Organometallic Chemistry Author(s): Ross J. Beattie, Andrew D. Sutton, Brian L. Scott, David L. Clark, Jaqueline L. Kiplinger, John C. Gordon The sterically encumbered NacNac ligand, [HC(MeCNAr)2]− (Ar = 2,6-i-Pr2C6H3), was investigated as a platform for supporting Lu-halide complexes, sought for their potential capability of being further converted into hydrocarbyl derivatives via metathetical chemistries with alkali metal alkyls. These substituted analogs were targeted as potentially viable candidates for alkane elimination chemistries, with a...
Source: Journal of Organometallic Chemistry - January 6, 2018 Category: Chemistry Source Type: research

Selective dimerization of terminal acetylenes in the presence of PEPPSI precatalysts and relative chloro- and hydroxo-bridged N-heterocyclic carbene palladium dimers
Publication date: Available online 3 January 2018 Source:Journal of Organometallic Chemistry Author(s): Sylwia Ostrowska, Natalia Szymaszek, Cezary Pietraszuk Highly regio- and stereoselective dimerization of terminal acetylenes occurs in the presence of [PdCl2(IPr)(3-chloropyridine)], other members of the family of PEPPSI precatalysts and the structurally related N-heterocyclic carbene palladium dimers, i.e. [{Pd(μ–Cl)Cl(IPr)}2] and [{Pd(μ–OH)Cl(IPr)}2] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). The reaction leads to exclusive formation of E-isomer of head to head dimerization product...
Source: Journal of Organometallic Chemistry - January 4, 2018 Category: Chemistry Source Type: research

Oxidation of olefins catalyzed by half-sandwich osmium(II) arene complexes
Publication date: Available online 3 January 2018 Source:Journal of Organometallic Chemistry Author(s): Joel M. Gichumbi, Bernard Omondi, Holger B. Friedrich Ten complexes [(η6-(arene)OsCl(C5H4N-2-CH=N-C6H5X)]PF6 (with arene = p-cymene (1) or benzene (2); X = 4-F (a), 4-Cl (b), 4-Br (c), 4-I(d) and 4–methyl (e)) were synthesized by reacting the corresponding N,N′-bidentate ligands with the osmium arene dimers [(η6-arene)Os(μ-Cl)Cl]2 in a 2:1 ratio. Complexes 1a-e and 2c-d are new. The compounds were fully characterized via 1H and 13C NMR, IR and UV–Vis spectroscopy, and elemental analy...
Source: Journal of Organometallic Chemistry - January 4, 2018 Category: Chemistry Source Type: research

New diorganotin(IV) complexes of salicylaldehyde based hydrazones bearing furan heterocycle moiety: X-ray structural investigation of dimethyltin(IV) and diphenyltin(IV) complexes
Publication date: Available online 4 January 2018 Source:Journal of Organometallic Chemistry Author(s): Sundeep Kumar, Mala Nath Some new diorganotin(IV) derivatives formulated as R2SnL (where R = Me, Bu, Ph and Oct) were obtained upon treatment of diorganotin(IV) precursors with acylhydrazones [H2La = N'-(2-hydroxy-3-methoxybenzylidene)furan-2-carbohydrazide, H2Lb = N'-(5-chloro-2-hydroxy-benzylidene)furan-2-carbohydrazide and H2Lc = N'-(2-hydroxy-5-nitrobenzylidene)furan-2-carbohydrazide] derived from Schiff base condensation of furan-2-carbohydrazide and substituted salicylaldehydes in methanol in appro...
Source: Journal of Organometallic Chemistry - January 4, 2018 Category: Chemistry Source Type: research

A tetranuclear diphenyltin(IV) complex and its catalytic activity in the aerobic Baeyer-Villiger oxidation of cyclohexanone
Publication date: Available online 4 January 2018 Source:Journal of Organometallic Chemistry Author(s): Susanta Hazra, Nuno M.R. Martins, Kamran Mahmudov, Fedor I. Zubkov, M.F.C. Guedes da Silva, Armando J.L. Pombeiro The synthesis and crystal structure of the new tetranuclear diphenyltin(IV) compound [{SnPh2}{SnPh2(OCOMe)}(μ2-OMe)(μ3-O)]2 (1), generated from the reaction of [SnPh2Cl2] and NaOCOMe, are described. Single crystal X-ray diffraction revealed that 1 is a tetranuclear complex with four diphenyltin(IV) units which are inter-connected by μ3-oxido and μ2-methoxido bridges leading to a ladder-like Sn4O4...
Source: Journal of Organometallic Chemistry - January 4, 2018 Category: Chemistry Source Type: research

Di(tert-butyl)aluminum, -gallium and -indium β-diketonates and β-diketiminates, reactions with oxygen and formation of an unprecedented peroxo-rich hexaperoxotriindium compound
Publication date: Available online 4 January 2018 Source:Journal of Organometallic Chemistry Author(s): Barun Jana, Christian Honaker, Werner Uhl Reactions of 1,3-di (tert-butyl)acetylacetone (2,2,6,6-tetramethyl-3,5-heptanedione), ( t Bu2acac)H, with tri (tert-butyl)aluminum, -gallium and -indium afforded selectively the corresponding di (tert-butyl)metal derivatives ( t Bu2acac)M t Bu2 [M = Al (1), Ga (2), In (3)] by release of isobutane. Likewise, diphenyl-β-diketamine [Ph–NC (Me)]2CH2, (Ph2nacnac)H, reacted with M t Bu3 to generate the compounds (Ph2nacnac)M t Bu2 [M = Ga (4), In (5)], which represe...
Source: Journal of Organometallic Chemistry - January 4, 2018 Category: Chemistry Source Type: research

Enantioselective copper-catalyzed conjugate additions of in situ generated organozirconium reagents to N-heterocyclic Michael acceptors
Publication date: Available online 4 January 2018 Source:Journal of Organometallic Chemistry Author(s): Ivana Némethová, Stanislav Bilka, Radovan Šebesta Stereoselective conjugate additions of organometallic reagents provide access to many useful chiral compounds. In this work, we have studied the enantioselective Cu-catalyzed conjugate addition of organozirconium reagents, which were generated in situ by hydrozirconation of alkenes. We show that N-heterocyclic Michael acceptors, represented by unsaturated lactams and 2,3-dihydropyridin-4(1H)-ones can be useful substrates for Cu-catalyzed conjugate ad...
Source: Journal of Organometallic Chemistry - January 4, 2018 Category: Chemistry Source Type: research

How to tame a palladium terminal imido
Publication date: Available online 3 January 2018 Source:Journal of Organometallic Chemistry Author(s): Annette Grünwald, Dominik Munz Palladium terminal imido complexes hold promise as catalysts for the amination of CH bonds. This computational study elucidates the electronic structure of palladium(II) and palladium(IV) terminal imido complexes by CASSCF as well as DFT calculations. In search of stable palladium terminal imido complexes, a series of synthetically relevant ancillary ligands are evaluated computationally. The thermodynamic stability of the palladium(II) complexes is correlated with the singlet/triplet...
Source: Journal of Organometallic Chemistry - January 3, 2018 Category: Chemistry Source Type: research

Deposited zirconocene chloride on silica-layered CuFe2O4 as a highly efficient and reusable magnetically nanocatalyst for one-pot Suzuki-Miyaura coupling reaction
Publication date: Available online 30 December 2017 Source:Journal of Organometallic Chemistry Author(s): Behzad Zeynizadeh, Farhad Sepehraddin The novel core-shell magnetically nanoparticles of CuFe2O4@SiO2@ZrCp2Clx (x: 0–2) were synthesized and used as a highly efficient catalyst for Suzuki-Miyaura coupling reaction of various aryl halides with phenylboronic acid. The reactions were carried out in PEG-400 (70 °C) to afford biaryls in high to excellent yields. The core-shell nanocomposite was easily separated from the reaction by an external magnet and reused for 5 times without significant loss of its cataly...
Source: Journal of Organometallic Chemistry - December 31, 2017 Category: Chemistry Source Type: research

Highly active mono and bis-ligated iminopyridyl nickel catalysts for 1-hexene reactions
Publication date: Available online 29 December 2017 Source:Journal of Organometallic Chemistry Author(s): Guangzhi Song, Lihua Guo, Qing Du, Wenyu Kong, Weimin Li, Zhe Liu A series of mono- and bis-ligated iminopyridyl Ni(II) catalysts were prepared and characterized. The activation of these Ni(II) complexes with methylaluminoxane generated the toluene alkylation by the hexene monomers, dimers and trimmers with high activities using only 1-hexene as feedstock. Most interestingly, The bis-ligated iminopyridyl Ni(II) catalysts demonstrated much better thermal stability and showed higher activities at high temperature than t...
Source: Journal of Organometallic Chemistry - December 30, 2017 Category: Chemistry Source Type: research

Hydrocarbon functionalization on palladium compounds in acidic solutions (a historical review) ∗
Publication date: Available online 30 December 2017 Source:Journal of Organometallic Chemistry Author(s): Elisey S. Rudakov, Georgiy B. Shul'pin The first Russian works in the area of palladium-stimulated functionalization of C‒H compounds in acidic media have been carried out mainly in Donetsk (Rudakov), as well as in Chernogolovka (Shilov, Shteinman), and Moscow (Moiseev, Yatsimirskiy, Ryabov, Shul'pin). A substantial difference of the oxidation of arenes and alkanes was found. Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - December 30, 2017 Category: Chemistry Source Type: research

Dual reactivity pattern of Mn(I) carbyne complexes Cp(CO)2Mn+ ≡C–R (R = Ar, Alk) vs. dppm: Subtle balance between double intramolecular nucleophilic addition and nucleophilic addition followed by migratory CO insertion
Publication date: Available online 28 December 2017 Source:Journal of Organometallic Chemistry Author(s): Dmitry A. Valyaev, Kamil I. Utegenov, Vassily V. Krivykh, Jérémy Willot, Nikolai A. Ustynyuk, Noël Lugan The Mn(I) cationic carbyne complexes [Cp(CO)2Mn+≡C–R]BX4 (R = Ph, Tol, Me, Bn; X = F, Cl, Ph) react with bis(diphenylphosphino)methane to afford selectively either cyclic λ5-1,3-diphosphetium semi-ylides [RC–P+Ph2CH2P+Ph2)]BPh4 ([R 4]BPh4; R = Ph, Tol), or Mn(I) complexes [Cp(CO)Mn(η3-(P,C,C)-Ph2PCH2P+Ph2C(R)=C=O)]BX4 ([R 5]BX4; R = Me, X = Ph; R...
Source: Journal of Organometallic Chemistry - December 29, 2017 Category: Chemistry Source Type: research

Multiple roles of silver salts in palladium-catalyzed C –H activations
Publication date: Available online 27 December 2017 Source:Journal of Organometallic Chemistry Author(s): Katherine L. Bay, Yun-Fang Yang, K.N. Houk Many Pd-catalyzed C–H functionalization reactions utilize stoichiometric Ag(I)-salts as additives. Ag additives are typically used either as a terminal oxidant or as a halide scavenger for Pd catalyst regeneration. However, recent experimental and computational studies have shown that Ag(I)-salts may play additional roles in C–H activation processes. Notably, cooperative Pd–Ag bimetallic C–H activations and Ag(I)-mediated Pd-catalyzed C–H arylati...
Source: Journal of Organometallic Chemistry - December 28, 2017 Category: Chemistry Source Type: research

Novel titanium(IV) complexes stabilized by 2-hydroxybenzyl alcohol derivatives as catalysts for UHMWPE production
Publication date: Available online 27 December 2017 Source:Journal of Organometallic Chemistry Author(s): Vladislav A. Tuskaev, Svetlana C. Gagieva, Dmitry A. Kurmaev, Sergey V. Zubkevich, Nikolay A. Kolosov, Evgenii K. Golubev, Galina G. Nikiforova, Victor N. Khrustalev, Boris M. Bulychev A series of titanium (IV) complexes (2, 5-7) stabilized by a substituted 2-hydroxybenzyl alcohols (1, 4) – were synthesized. Structures of complexes 6-7 were determined by X-ray diffraction. Titanium atom in the tetrameric complex 6 has an octahedral environment created by chlorine atom and five oxygen atoms. The main structural f...
Source: Journal of Organometallic Chemistry - December 28, 2017 Category: Chemistry Source Type: research

Synthesis and fluorescence of 3,4,6,7,8,9-hexaphenyl-1H-benzo[g]isochromen-1-one
Publication date: Available online 27 December 2017 Source:Journal of Organometallic Chemistry Author(s): Dmitry A. Loginov, Alexander P. Molotkov, Nikolay E. Shepel Highly step- and atom-economic synthetic route to 3,4,6,7,8,9-hexaphenyl-1H-benzo[g]isochromen-1-one (1) based on the rhodium catalyzed reaction of terephthalic acid with diphenylacetylene was developed. The best catalytic system for this reaction is [CpRhI2]n/Cu(OAc)2. Compound 1 shows fluorescent properties with a strong Stokes shift. Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - December 28, 2017 Category: Chemistry Source Type: research

Octupolar organometallic Pt(II) NCN-pincer complexes; Synthesis, electronic, photophysical, and NLO properties
Publication date: Available online 28 December 2017 Source:Journal of Organometallic Chemistry Author(s): Guido D. Batema, Cornelis A. van Walree, Gerard P.M. van Klink, Celso de Mello Donegá, Andries Meijerink, Javier Perez-Moreno, Koen Clays, Gerard van Koten A series of organometallic octupolar 1,3,5-substituted-2,4,6-styryl-benzene complexes was synthesized by post-modification of parent [PtCl(NCN-CHO-4)], i.e. 1,3,5-tri-R-2,4,6-tris[(4-(PtCl)(3,5-bis[(dimethylamino)methyl]styryl)]benzene (NCN = [C6H2(CH2NMe2)2-2,6]– in which R = OMe, H, Br (1–3). Their synthesis involved a triple Horner-Wad...
Source: Journal of Organometallic Chemistry - December 28, 2017 Category: Chemistry Source Type: research

A novel tridentate [ONS] binuclear titanium complex bearing oxo-bridged macrocyclic structure for ethylene polymerization
Publication date: Available online 25 December 2017 Source:Journal of Organometallic Chemistry Author(s): Li Zhang, Xiong Chen, Xiao Xiao, Derong Luo, Yi Zeng, Tingcheng Li, Xiangdan Li, Aiqing Zhang, Guangyong Xie A novel xanthene-bridged bissalicylaldiminato tridentate [ONS] ligand ligated binuclear titanium complex Ti 2 L bearing oxo-bridged macrocyclic structure were synthesized and characterized by 1H NMR, IR and elemental analysis. This binuclear complex Ti 2 L was also investigated by single-crystal X-ray diffraction, which demonstrated C2 symmetric structure with each titanium coordinated with six atoms and formed...
Source: Journal of Organometallic Chemistry - December 26, 2017 Category: Chemistry Source Type: research

Binuclear luminescent Pt(II) complexes based on substituted 3,6-diphenylpyridazines; synthesis and photophysical study
Publication date: Available online 26 December 2017 Source:Journal of Organometallic Chemistry Author(s): Daniil D. Zhukovsky, Vladimir V. Sizov, Galina L. Starova, Sergey P. Tunik, Elena V. Grachova Seven novel binuclear Pt (II) metalated complexes based on substituted 3,6-diphenylpyridazines have been synthesized and structurally characterized using XRD crystallography, NMR spectroscopy and HR ESI mass-spectrometry. Three of these complexes contain two {Pt (CˆN)} metalated fragments located at diphenylpyridazine, the square-planar environment at platinum centres are completed with two terminal and one bridging chlo...
Source: Journal of Organometallic Chemistry - December 26, 2017 Category: Chemistry Source Type: research

Nickel complexes supported by selenium-based tridentate ligands and their use as effective catalyst systems for ethylene dimerisation
Publication date: Available online 24 December 2017 Source:Journal of Organometallic Chemistry Author(s): Lucielle C. Dresch, Carlos H. Junges, Osvaldo de L. Casagrande, Rafael Stieler A series of nickel(II) bromide complexes, [NiBr2(SeˆOˆN)] (Ni1–Ni4), supported by selenium-based tridentate ligands were prepared in good yields by reacting arylselenyl-ether-pyrazolyl ligands (L1–L4) with NiBr2(DME) (DME = 1,2-dimethoxyethane). All complexes were characterised by infrared spectroscopy, elemental analysis and high-resolution mass spectrometry. The crystallisation of Ni2 in THF/Et2O leads to the for...
Source: Journal of Organometallic Chemistry - December 25, 2017 Category: Chemistry Source Type: research

Ferrocenyl chalcone-based Schiff bases and their metal complexes: Highly efficient, solvent-free synthesis, characterization, biological research
This study highlights the synthesis and characterization of Schiff base ligands namely 1-ferrocenyl-3- (2-furyl) propenone diamino (thio) urea and selected metal complexes including Pb(Ⅱ), Bi(Ⅲ), Cu(Ⅱ), Cr(Ⅲ), Ba(Ⅱ), Cd (Ⅱ), Fe(Ⅱ), Ni(Ⅱ), Sn(Ⅱ), Nd(Ⅱ) as a central metal. The stoichiometric ratios of the prepared complexes were estimated using complementary techniques such as elemental analyses (C,H,N), FT-IR and molar conductivity. Furthermore, their physicochemical studies were carried out using thermal TGA. Antimicrobial activities of both the Schiff base ligand and its metal complexes were tested aga...
Source: Journal of Organometallic Chemistry - December 22, 2017 Category: Chemistry Source Type: research

Effect of α- and β-H/F substitution on the homolytic bond strength in dormant species of controlled radical polymerization: OMRP vs. ITP and RAFT
Publication date: Available online 20 December 2017 Source:Journal of Organometallic Chemistry Author(s): Rinaldo Poli, S.M.Wahidur Rahaman, Vincent Ladmiral, Bruno Ameduri The X-C bond dissociation energies (BDEs) for five series of X-CH2-n F n CH3-m F m molecules (n = 0, 1, 2; m = 0, 1, 2, 3) with X = H, I, SC(S)OEt, Co(acac)2 or Mn(CO)5 were calculated using a DFT approach, yielding results in good agreement with the few experimentally determined values (X = H and I). Calculations were also carried out on the simpler (CO)5Mn-CF n H3-n molecules (n = 0, 1, 2, 3), for which experimental data are avail...
Source: Journal of Organometallic Chemistry - December 20, 2017 Category: Chemistry Source Type: research

Design and syntheses of a new family of palladium complexes derived from tridentate ligands and their application as catalysts for Suzuki-Miyaura cross-coupling reactions
Publication date: Available online 14 December 2017 Source:Journal of Organometallic Chemistry Author(s): Anand Ratnam, Manju Bala, Rajan Kumar, U.P. Singh, Kaushik Ghosh Palladium complexes [Pd(L1−5) (PPh3)]ClO4 (LnH (n = 1–5, H = phenolic dissociable proton) (1–5)) were synthesised and characterised by different spectroscopic methods like 1H NMR, IR and UV- visible spectral studies. The molecular structure of the representative complex [Pd(L2) (PPh3)]ClO4 (2) was determined by X-ray crystallography. These new complexes were utilised to study Suzuki-Miyaura cross-coupling reactions. Substituted ...
Source: Journal of Organometallic Chemistry - December 16, 2017 Category: Chemistry Source Type: research

Organotin(IV) 4-(benzo[d][1,3]dioxol-5-ylmethyl)piperazine-1-carbodithioates: Synthesis, characterization and biological activities
Publication date: Available online 14 December 2017 Source:Journal of Organometallic Chemistry Author(s): Farzana Shaheen, Muhammad Sirajuddin, Saqib Ali, Zia-ur-Rehman, Paul J. Dyson, Naseer Ali Shah, Muhammad Nawaz Tahir A series of organotin(IV) derivatives R3SnL (1–3), R2SnLCl (4–6) and R2SnL2 (7–9) (where R = Me, Bu, Ph and L = 4-(benzo[d][1,3]dioxol-5-ylmethyl)piperazine-1-carbodithioate) were prepared from the reaction of 4-(benzo[d][1,3]dioxol-5-ylmethyl)piperazine-1-carbodithioate (L-salt) with the corresponding triorganotin(IV) chlorides and diorganotin(IV) dichlorides. All compounds we...
Source: Journal of Organometallic Chemistry - December 16, 2017 Category: Chemistry Source Type: research

Reaction of allyl bromide with cyclometallated platinum(II) complexes: Unusual kinetic behavior and a novel case of methyl and allyl C-C bond reductive elimination
Publication date: Available online 15 December 2017 Source:Journal of Organometallic Chemistry Author(s): Mahboobeh Zanganeh, S. Jafar Hoseini, Mehdi Rashidi, S. Masoud Nabavizadeh, Mohammad Reza Halvagar Reaction of the known cyclometallated platinum(II) complexes [PtMe(CˆN)(PPh2Me)], in which CˆN is either 2-phenylpyridinate (abbreviated as ppy-H), 1a, or benzo-h-quinolate (abbreviated as bhq-H), 1b, with excess allyl bromide, CH2=CH-CH2Br, in acetone gave the thermodynamic Pt(IV) product complex cis-[PtMe(CH2-CH=CH2)Br(ppy-H)(PPh2Me)], 2a, or cis-[PtMe(CH2-CH=CH2)Br(bhq-H)(PPh2Me)], 2b, respectively, in which...
Source: Journal of Organometallic Chemistry - December 16, 2017 Category: Chemistry Source Type: research

Ferrocenealkylsilane molecular rectifiers
Publication date: Available online 16 December 2017 Source:Journal of Organometallic Chemistry Author(s): Angela D. Broadnax, Zachary A. Lamport, Ben Scharmann, Oana D. Jurchescu, Mark E. Welker We developed four new ferrocene containing alkylated silane self-assembled monolayers (SAMs), and evaluated their electrical properties in a metal/SAM/metal configuration. The ferrocenyl silanes used in this work can be prepared in one to two simple chemical steps from readily available ferrocene carboxaldehyde. We found that the molecular diodes obtained from these molecules can exhibit current rectification ratios as high as 150...
Source: Journal of Organometallic Chemistry - December 16, 2017 Category: Chemistry Source Type: research

Phosphinomethylation of [1 ′-(diphenylphosphino)ferrocenyl]-methylamines as a route to unsymmetric ferrocene diphosphine ligands
Publication date: 15 January 2018 Source:Journal of Organometallic Chemistry, Volume 855 Author(s): Ondřej Bárta, Ivana Císařová, Petr Štěpnička [1′-(Diphenylphosphino)ferrocenyl]methylamine (1) reacts with Ph2PH/(CH2O)x or [Ph2P(CH2OH)2]Cl to give mixtures of Ph2PfcCH2NHCH2PPh2 and Ph2PfcCH2N(CH2PPh2)2 in which the triphosphine dominates (fc = ferrocene-1,1′-diyl). To avoid unwanted two-fold phosphinomethylation, the amine group in 1 was alkylated. As expected, the reaction of the N-methyl analogue Ph2PfcCH2NHMe (5), obtained by reductive methylation of the aldehyde P...
Source: Journal of Organometallic Chemistry - December 16, 2017 Category: Chemistry Source Type: research

Insertion of the N,B,N-chelated germylene into P-Cl Bond(s) in selected chlorophosphines
Publication date: Available online 13 December 2017 Source:Journal of Organometallic Chemistry Author(s): Jiří Böserle, Roman Jambor, Aleš Růžička, Libor Dostál The reaction of the N,B,N-chelated germylene [(i-Pr)2NB(NDmp)2]Ge (1) (where Dmp = 2,6-Me2C6H3) with Ph2PCl in 1:1 M ratio led to a smooth insertion into the P-Cl bond under formation of [(i-Pr)2NB(NDmp)2]Ge(PPh2)Cl (2). Similarly, the treatment of 1 with RPCl2 in 2:1 M ratio resulted in double insertion products {[(i-Pr)2NB(NDmp)2]GeCl}2(PR) [where R = Ph (3) or t-Bu (4)]. The products were characterized...
Source: Journal of Organometallic Chemistry - December 14, 2017 Category: Chemistry Source Type: research

Iridium complexes with aliphatic, non-innocent pincer ligands
Publication date: Available online 13 December 2017 Source:Journal of Organometallic Chemistry Author(s): Alexey V. Polukeev, Ola F. Wendt Pincer complexes attract considerable attention both as interesting objects for fundamental studies and efficient catalysts. This mini-review describes a relatively new offshoot of the field – namely, the chemistry of iridium complexes with aliphatic PCsp3P non-innocent pincer ligands. High flexibility, often combined with possibility to activate internal C–H bonds, offers several new patterns of metal-ligand cooperation; some of them were successfully used in catalysis of ...
Source: Journal of Organometallic Chemistry - December 14, 2017 Category: Chemistry Source Type: research

Syntheses, structures and immobilization of ruthenium complexes bearing N,O-Schiff-base or N,N ′-diamine ligands functionalized with alkoxysilyl groups
Publication date: Available online 12 December 2017 Source:Journal of Organometallic Chemistry Author(s): Ai-Quan Jia, Li-Miao Shi, Fule Wu, Zhi-Feng Xin, Qian-Feng Zhang Condensation of γ-aminopropyltriethoxysilane and substituted salicylaldehydes in ethanol afforded three new Schiff-base compounds [(EtO)3Si(CH2)3N=CHArOH] (Ar = C6H4, L1H; C6H3(4-Cl), L2H; C6H2(2,4- t Bu2), L3H). Treatment of [Ru(NO)Cl3⋅xH2O] with L1H in the presence of Et3N in THF gave a ruthenium nitrosyl complex [RuCl2(NO)(κ2-O,N-L1)(OEt2)] (1) with a linear N≡O moiety. Reactions of [(η 6-p-cymene)RuCl(μ-Cl)]2 with L1H or...
Source: Journal of Organometallic Chemistry - December 13, 2017 Category: Chemistry Source Type: research

Sodium naphthalenide reduction of 1,3 –diphenyl–6–(tert-butyl) fulvene: Stabilizing Eu2+ with a sterically demanding ansa–ligand framework
Publication date: Available online 12 December 2017 Source:Journal of Organometallic Chemistry Author(s): Sonya K. Adas, Gary J. Balaich Stereoselective syntheses of three new rac di–(tert–butyl)ethano bridged metallocene compounds of Yb, Eu and Sm were carried out by a unique strategy involving hydrocarbon radical anion coupling of a trisubstituted pentafulvene followed by incorporation of the metal by K+ salt metathesis reactions. Reductive coupling of 1,3–diphenyl–6–(tert-butyl) fulvene with sodium naphthalenide gave the corresponding bis(cyclopentadiene) ansa–ligand precursor rac&nd...
Source: Journal of Organometallic Chemistry - December 13, 2017 Category: Chemistry Source Type: research

Synthesis and characterization of diruthenaborane analogues of pentaborane(11) and hexaborane(10)
Publication date: Available online 11 December 2017 Source:Journal of Organometallic Chemistry Author(s): Benson Joseph, Suman Gomosta, Subrat Kumar Barik, Soumya Kumar Sinha, Thierry Roisnel, Vincent Dorcet, Jean-François Halet, Sundargopal Ghosh In an attempt to synthesize expanded-cage metallaheteroboranes containing heavier chalcogen atoms, the reaction of diruthenaborane analogue of pentaborane(9), nido-[1,2-(Cp*RuH)2B3H7] (1) with phenyl-chalcogenoborates Li[BH3(EPh)] (E = S, Se or Te) was carried out. Thermolysis of nido-1 with Li[BH3(SPh)] led to the formation of the dimetalla-pentaborane(11) anal...
Source: Journal of Organometallic Chemistry - December 12, 2017 Category: Chemistry Source Type: research

Two-photon absorption properties of four new pentacoordinated diorganotin complexes derived from Schiff bases with fluorene
Publication date: Available online 11 December 2017 Source:Journal of Organometallic Chemistry Author(s): Alejandro Enríquez-Cabrera, Alberto Vega-Peñaloza, Violeta Álvarez-Venicio, Margarita Romero-Avila, Pascal G. Lacroix, Gabriel Ramos-Ortiz, Rosa Santillan, Norberto Farfán In this paper we report the synthesis and characterization of four novel pentacoordinated diorganotin complexes, obtained through a methodology that involves a multicomponent reaction of 4-([9H-fluorene-2-yl]ethynyl)-2-hydroxybenzaldehyde, 2-amino-5-nitrophenol and diphenyl or dibutyl-tin oxides. Diorganotin complexes 8&n...
Source: Journal of Organometallic Chemistry - December 12, 2017 Category: Chemistry Source Type: research

Key mechanistic insights into the intramolecular C-H bond amination and double bond aziridination in sulfamate esters catalyzed by dirhodium tetracarboxylate complexes
Publication date: Available online 11 December 2017 Source:Journal of Organometallic Chemistry Author(s): Adrián Varela-Álvarez, Brandon E. Haines, Djamaladdin G. Musaev Density Functional Theory was used to study the mechanisms of intramolecular C-H amination and olefin aziridination reactions of a variety of sulfamate esters. Particular emphasis is placed on the mechanism and factors governing amination of primary, secondary, tertiary and benzylic C-H bonds, the competition between tertiary and benzylic C-H amination, and the competition between allylic C-H amination and olefin aziridination. In these stud...
Source: Journal of Organometallic Chemistry - December 12, 2017 Category: Chemistry Source Type: research

Laying the way to meta-functionalization of naphthalene proton sponge via the use of Schlosser's superbase
Publication date: Available online 12 December 2017 Source:Journal of Organometallic Chemistry Author(s): Alexander S. Antonov, Victor G. Bardakov, Alexander F. Pozharskii, Mikhail A. Vovk, Alexander D. Misharev Lithiation of 1,8-bis(dimethylamino)naphthalene (DMAN) with Schlosser's superbase (n-BuLi–t-BuOK) in the presence of TMEDA in hexane was examined. It has been shown that, compared with previously studied n-BuLi–TMEDA or t-BuLi–TMEDA mixtures, this reagent provides much more selective meta-lithiation. A variety of 3-substituted and 3,6-disubstituted derivatives of DMAN has been prepared in a good ...
Source: Journal of Organometallic Chemistry - December 12, 2017 Category: Chemistry Source Type: research