Mechanistic insights into asymmetric reductive coupling of isoquinolines by a chiral diboron with DFT calculations
We report our complete mechanistic study on the highly diastereo- and enantioselective reductive coupling of isoquinoline templated by a chiral diboron. An uncommon activation mode, activation of the B-B bond via double N-B coordination followed by [3,3]-sigmatropic migration was computed to be more preferable over the radical pathway involving the B-B bond homolysis. On the basis of this mechanism, origins of the excellent enantio- and chemoselectivity were found to be driven by less steric repulsion and more secondary orbital interactions in the most favorable reductive coupling transition state. The reductive coupling o...
Source: Journal of Organometallic Chemistry - February 6, 2018 Category: Chemistry Source Type: research

Michael addition of cyclic β-oxo ester and α-methyl cyano ester substrates with activated olefins by iron complexes of benzimidazole derived N-heterocyclic carbene ligands
Publication date: Available online 5 February 2018 Source:Journal of Organometallic Chemistry Author(s): A.P. Prakasham, Manoj Kumar Gangwar, Prasenjit Ghosh Michael addition reactions of cyclic β-oxo ester and α-methyl cyano ester substrates with acceptor activated olefins were catalyzed by iron N−heterocyclic carbene (NHC) complexes of the type, {Cp[1-benzyl-3-alkyl-benzimidazol-2-ylidene]Fe(CO)2}I, where [alkyl = i-Pr (1) and Et (2)] in the presence of l-proline as chiral auxiliary under ambient conditions. In case of the cyclic β-oxo ester substrates good yields of up to 68% and enantioselect...
Source: Journal of Organometallic Chemistry - February 6, 2018 Category: Chemistry Source Type: research

Synthesis, antiproliferative activity and apoptosis-promoting effects of arene ruthenium(II) complexes with N, O chelating ligands
Publication date: Available online 3 February 2018 Source:Journal of Organometallic Chemistry Author(s): Nanjan Mohan, Mohamed Kasim Mohamed Subarkhan, Rengan Ramesh New half sandwich arene ruthenium(II) complexes of the type [Ru(arene)Cl(L)] (where arene = benzene and p-cymene, L = thiophene benzhydrazone ligands) have been synthesized from the reactions of the neutral precursor [Ru(arene) (μ-Cl) Cl]2 and the corresponding benzhydrazone ligand. All the complexes were completely characterized by elemental analysis and additionally by IR, UV–Vis, 1H NMR and ESI-MS spectroscopic methods. The solid state str...
Source: Journal of Organometallic Chemistry - February 4, 2018 Category: Chemistry Source Type: research

The metallostibine Os2(CO)8( μ-SbPh): A versatile donor precursor for antimony-containing heterometallic clusters
Publication date: 1 March 2018 Source:Journal of Organometallic Chemistry, Volume 858 Author(s): Ying-Zhou Li, Rakesh Ganguly, Deborah Roshni Rajaratnam, Weng Kee Leong The metallostibine Os2(CO)8(μ-SbPh), 2, acts as a good two-electron donor ligand, reacting readily with Group 8 metal carbonyls to give heterometallic clusters. Specifically, it undergoes ligand substitution reaction with Fe2(CO)9, Os3(CO)11(CH3CN), or Os3(CO)10(CH3CN)2 to afford Os2Fe(CO)12(μ 3-SbPh), 3, Os5(CO)19(μ 3-SbPh), 4, or Os7(CO)26(μ 3-SbPh)2, 5, respectively, in moderate to high yields. An analogous reaction with Ru3(CO)11(CH3CN) aff...
Source: Journal of Organometallic Chemistry - February 4, 2018 Category: Chemistry Source Type: research

Origin of β-agostic interaction in d0 transition metal alkyl complexes: Influence of ligands
Publication date: Available online 3 February 2018 Source:Journal of Organometallic Chemistry Author(s): Shyama Ramakrishnan, Eluvathingal D. Jemmis Classical picture of agostic interaction involves a three-center two-electron interaction where the metal center has valence electron count less than sixteen. Though unsaturation on metal center is a necessary condition, it is not sufficient to show agostic interaction. For example, TiEtCl3 and its diphosphine adduct TiEtCl3(dmpe) have d0-metal center and the electron count is far less from 18 electrons for both. But TiEtCl3 shows no agostic interaction while TiEtCl3(dmpe) ha...
Source: Journal of Organometallic Chemistry - February 3, 2018 Category: Chemistry Source Type: research

Group 9 metallatelluraboranes: Comparison with their sulfur analogues
Publication date: Available online 3 February 2018 Source:Journal of Organometallic Chemistry Author(s): Amr A.A. Attia, Alexandru Lupan, R. Bruce King The lowest energy structures for the Group 9 metallachalcaboranes CpMEB n-2H n-2 (M = Co, Rh, Ir; E = S, Te) are found by density functional theory to have a central closo MEB n–2 deltahedron consistent with their 2n + 2 skeletal electrons. Structures having metal atoms at degree 5 vertices and sulfur atoms at degree 4 vertices are clearly energetically preferred. However, for the 9- and 10-vertex metallatelluraboranes CpMTeB n–2H n–2 (n...
Source: Journal of Organometallic Chemistry - February 3, 2018 Category: Chemistry Source Type: research

Labile η6-areneruthenium sulfide clusters. Crystal structure of [(C6H6)4Ru5S4](PF6)2 and [(C6H6)4Ru4S5](PF6)2
Publication date: Available online 3 February 2018 Source:Journal of Organometallic Chemistry Author(s): V.S. Korenev, P.A. Abramov, N.B. Kompankov, A.L. Gushchin, D.G. Sheven, M.N. Sokolov A new labile areneruthenium sulfide complex, [(C6H6)3Ru3S2](PF6)2 (1), was prepared and characterized both in solid state and in solution. Light-driven de-coodination of the arene ligands has been demonstrated. Two new polynuclear areneruthenium complexes, [(C6H6)4Ru5S4](PF6)2·2CH3CN (2) and [(C6H6)4Ru4S5](PF6)2·1.25CH3CN·0.5H2O (3), were obtained from 1 and structurally characterized. Redox behaviour of [(C6H6)3Ru...
Source: Journal of Organometallic Chemistry - February 3, 2018 Category: Chemistry Source Type: research

Computational exploration of reactive fragment for mechanism-based inhibition of xanthine oxidase
Publication date: Available online 3 February 2018 Source:Journal of Organometallic Chemistry Author(s): Ye Du, Ziye Liu, Fangfang Qiao, Shunyang Wang, Kai Chen, Xinhao Zhang The xanthine oxidase (XO) family is a group of molybdenum-containing enzymes that catalyze the transfer of an oxygen atom from water to a substrate, such as xanthine or aldehyde. The proposed mechanism for the reductive half-reaction of xanthine oxidase involves nucleophilic addition of Mo-bound hydroxide to the substrate and hydride transfer from the substrate to sulfido group (Mo=S) at the molybdenum cofactor (Moco) reaction center. A DFT study of ...
Source: Journal of Organometallic Chemistry - February 3, 2018 Category: Chemistry Source Type: research

Coordination studies of nitrogen-containing aryl phosphine ligands P ˆN and PˆNˆN with rhodium
Publication date: Available online 3 February 2018 Source:Journal of Organometallic Chemistry Author(s): Katarzyna Wajda-Hermanowicz, Andrzej Kochel, Robert Wróbel The coordination behavior of the heterofunctional phosphine ligand PPh2NH(2-Py), PPh2(o-C6H4)CH=N-(CH2)nPh (n = 0–3) and PPh2(o-C6H4)CH=N-(CH2)n-(2-Py) (n = 1 or 2) towards Rh(I) and Rh(III) are reported and examples of neutral and cationic complexes containing bi-dentate PˆN or tri-dentate PˆNˆN and NˆNˆC chelating modes of coordination are found. The synthesized complexes were characterized using different analyti...
Source: Journal of Organometallic Chemistry - February 3, 2018 Category: Chemistry Source Type: research

Synthesis and characterization of mesoporous Pd(II) organometal nanoplatelet catalyst for copper-free Sonogashira reaction in water
Publication date: Available online 3 February 2018 Source:Journal of Organometallic Chemistry Author(s): Fengxia Zhu, Pusu Zhao, Qiaoqi Li, Didi Yang Periodic mesoporous organopalladium(II)-bridged silica with platelet morphology (Pd(II)-PMO-P) was synthesized by the co-condensation of TEOS and Pd[PPh2(CH2)2Si(OC2H5)3]2Cl2 using P123 as structure-directing agent. The as-made Pd(II)-PMO-P samples were characterized with XRD, BET, ICP, SEM, TEM, solid NMR, XPS, as well as FT-IR. It was found that these products were composed of platelets (300–400 nm) with short and straight mesoporous channels (100–200 nm). ...
Source: Journal of Organometallic Chemistry - February 3, 2018 Category: Chemistry Source Type: research

Abnormal NHC supported palladacycles: Regioselective arylation of heteroarenes via decarboxylation
We report synthesis of two new palladium(II) complexes of abnormal N-heterocyclic carbene ligands. The catalytic activity of these palladium(II) complexes was examined for the decarboxylative arylation of N-methylindole-carboxylic acids. An exclusive regioselectivity and very good yields were obtained with a variety of aryl halide partners. Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - February 3, 2018 Category: Chemistry Source Type: research

Synthesis and characterization of click-decahydrodecaborate derivatives by the copper(I) catalyzed [3+2] azide-alkyne cycloaddition reaction
Publication date: Available online 1 February 2018 Source:Journal of Organometallic Chemistry Author(s): Suzan El Anwar, Zahra Laila, Ron Ramsubhag, Sami Tlais, Ali Safa, Gregory Dudley, Daoud Naoufal A facile and rapid access to a wide range of novel 1,2,3-triazoles bearing closo-decahydrodecaborate anion [B10H10]2− has been developed through an efficient general synthetic approach. It is based on the nucleophilic cleavage of 2-tetrahydrofuranium decaborate with sodium azide to form the known [B10H9O(CH2)4N3]2−. This azide derivative obtained reacted with various linear alkynes (phenylacetylene, 5-chloro-1-pe...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

New Pt(II) complex with extra pure green emission for OLED application: Synthesis, crystal structure and spectral properties
Publication date: Available online 2 February 2018 Source:Journal of Organometallic Chemistry Author(s): Ilya Taidakov, Sergey Ambrozevich, Rasim Saifutyarov, Konstantin Lyssenko, Roman Avetisov, Elena Mozhevitina, Andrew Khomyakov, Mikhail Khrizanforov, Yulia Budnikova, Igor Avetissov New (2-(4-methylpyrazol-1-yl)phenyl) platinum(II) (dibenzoylmethane) Pt(mpp)(dbm) complex based on 4-methylpyrazole was synthesized using a simple scheme. Its crystal structure, spectral and electrochemical properties were studied. The extra pure green (CIE chromacity coordinates X = 0.1419, Y = 0.7444) electroluminescence for OLED ...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

Protic and substituted NCN palladium(II) pincer complexes with 1,3-bis(benzimidazol-2 ′-yl)-2-bromobenzenes: Structure and catalysis
Publication date: Available online 2 February 2018 Source:Journal of Organometallic Chemistry Author(s): Varsha Rani, Harkesh B. Singh, Ray J. Butcher A new class of sparingly soluble NCN palladium(II) pincer complexes of the type (N ˆ C ˆ N)PdBr: [Methyl(N ˆ C ˆ N)PdBr], C26H25N4PdBr (14), [Tosyl(N ˆ C ˆ N)PdBr], C38H33N4O4S2PdBr (15), [ Benzyl(N ˆ C ˆ N)PdBr], C38H33N4PdBr (16) and [Pentyl(N ˆ C ˆ N)PdBr], C34H41N4PdBr (17) [(N ˆ C ˆ N) = 5-tert-butyl-1,3-bis-(N-substituted-benzimidazol-2′-yl)phenyl] were synthesized by the treatment of palladium(0) p...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

Efficient N-heterocyclic carbene palladium(II) catalysts for carbonylative Suzuki-Miyaura coupling reactions leading to aryl ketones and diketones
Publication date: Available online 2 February 2018 Source:Journal of Organometallic Chemistry Author(s): Mansur Ibrahim, Imran Malik, Waseem Mansour, Muhammad Sharif, Mohammed Fettouhi, Bassam El Ali New N, N′-substituted imidazolium salts (L1 and L2) and their corresponding diiodopyridinepalladium(II) complexes (C1 and C2) were successfully synthesized and characterized. Reactions of palladium iodide with the newly synthesized N, N′-substituted imidazolium iodides in pyridine afforded the corresponding new palladium-N-heterocyclic carbene pyridine complexes in high yields. The new palladium(II) complex C1 was...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

Unexpected formation of nitroso-chelated cyclic η1-acylruthe-nium(II) complex, an effective catalysts for transfer hydrogenation reaction
Publication date: Available online 2 February 2018 Source:Journal of Organometallic Chemistry Author(s): Nirmalya Mukherjee, Rafał Gawin, Stefan Czarnocki, Roman Gajda, Maura Malińska, Krzysztof Woźniak, Anna Kajetanowicz, Grela Karol Reaction of commercial ruthenium complexes M31 and M20 with 2-nitrostyrene gave a new nitroso-chelated cyclic η1-acyl ruthenium(II) complexes Ru-4 and Ru-6 respectively instead of expected Hoveyda-Grubbs type (pre)catalyst Ru-3. New complexes were characterized by means of standard analytical techniques and their crystallographic structure has been confirmed by X-ray structural analys...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

Major differences between preferred tetracarbagallane and tetracarbalane structures
Publication date: Available online 2 February 2018 Source:Journal of Organometallic Chemistry Author(s): Amr A.A. Attia, Alexandru Lupan, R. Bruce King The complete series of tetracarbagallanes C4Ga n–4Me n (6 ≤ n ≤ 14) has been examined by density functional theory. The lowest-energy C4Ge6Me10 structure is a very symmetrical T d tetracapped octahedral structure with an adamantane-like surface very similar to the experimentally known R'4C4Ga6R6 structures and to the lowest energy structure for the tetracarbalane C4Al6Me10. This structure is the only lowest energy C4Ga n–4Me n (n = 6 to 14) st...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

Structure and vibrational spectroscopic study of phthalimido-functionalized N-heterocyclic palladium complexes. Correlations between structure and catalytic activity
Publication date: Available online 2 February 2018 Source:Journal of Organometallic Chemistry Author(s): János Mink, Serena L.M. Goh, Manuel P. Högerl, Fritz E. Kühn, Markus Drees, Judith Mihály, Csaba Németh, László Hajba New complexes of Pd(II) with cationic phthalimido-functionalized N-heterocyclic carbene (NHC), the cis-Diacetonitrile(chloro)[1-(2≷-phthalamidoethyl)-3-methylimidazolin-ylidene]palladium(II) Hexafluorophosphate (and its CD3CN derivative) had been successfully used as catalyst in the Suzuki–Miyaura cross-coupling reaction. This complex have been studie...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

Preparation of polydimethylsiloxane with amino end group via Pd-catalyzed dehydrogenative coupling of terminal hydrosilyl unit and amine
Publication date: Available online 2 February 2018 Source:Journal of Organometallic Chemistry Author(s): Feng-Tao Zheng, Takashi Kai, Zhou Lu, Kazuki Yamamoto, Joji Ohshita Ring-opening polymerization of hexamethylcyclotrisiloxane (D3) with organolithium reagents (R1Li) followed by quenching of the resulting anions with chlorodimethylsilane yielded the corresponding polysiloxanes with R1 and SiMe2H groups at each end. The hydrosilyl end groups readily underwent palladium-catalyzed dehydrogenative amination reactions with secondary amines (R2 2NH) to produce polysiloxanes with amino end groups, R1(SiMe2O) n SiMe2NR2 2. The...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

One-pot reaction for the synthesis of N-substituted 2-aminobenzoxazoles using triphenylbismuth dichloride as cyclodesulfurization reagent
Publication date: 15 March 2018 Source:Journal of Organometallic Chemistry, Volume 859 Author(s): Yuki Murata, Natsuho Matsumoto, Maya Miyata, Yuki Kitamura, Naoki Kakusawa, Mio Matsumura, Shuji Yasuike The treatment of various 2-aminophenols with isothiocyanates afforded thioureas, which were reacted in situ with triphenylbismuth dichloride in the presence of triethylamine to give the expected N-substituted benzoxazol-2-amines in good to excellent yields. Triphenylbismuth dichloride promoted the successful cyclodesulfurization of thioureas with short reaction times under mild reaction conditions. This reaction is the fir...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

2,6-Lutidine-linked bis-saturated NHC pincer ligands, silver complexes and transmetallation
Publication date: 15 March 2018 Source:Journal of Organometallic Chemistry, Volume 859 Author(s): Matthew Asay, Magdalena Quezada-Miriel, J. Rubén Ochoa-Sanfelice, Diego Martinez-Otero Pincer ligands have proven to be valuable tools in the formation of robust transition metal complexes. To date, pincer ligands have featured an extremely diverse array of structural motifs, backbones and donor units. Carbene ligands have been easily integrated into a variety of pincer ligand structures and yet there are very few examples in which saturated NHC donor moieties are featured. Saturated NHCs are known to have unique donor...
Source: Journal of Organometallic Chemistry - February 2, 2018 Category: Chemistry Source Type: research

Fast and transition metal-free general method for the preparation of chalcogenophosphates
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Junxing Wang, Xiaolong Wang, Hongjie Li, Jie Yan In the presence of Cs2CO3 and I2, the coupling reaction of dialkyl phosphites with dichalcogenides (S, Se and Te) proceeds efficiently and completes in several minutes under mild conditions, affording the corresponding chalcogenophosphates in moderate to good yields. This fast and transition metal-free procedure provides a general method for the preparation of chalcogenophosphates. Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - February 1, 2018 Category: Chemistry Source Type: research

Bonding and structural features of metal-metal bonded homo- and hetero-dinuclear complexes supported by unsaturated hydrocarbon ligands
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Hayato Tsurugi, Payel Laskar, Keishi Yamamoto, Kazushi Mashima Dinuclear complexes with a metal-metal interaction have been extensively investigated as minimum entities of metal clusters. Hydrocarbon-bridged dinuclear complexes are one of the most important class of the dinuclear complexes for exploring any transformations of the unsaturated hydrocarbons at the dinuclear core. In this review, we summarize the dinuclear complexes with metal-metal interaction supported by unsaturated hydrocarbons such as alkyne, dienes, ...
Source: Journal of Organometallic Chemistry - February 1, 2018 Category: Chemistry Source Type: research

First molecular conductors of BPDT-TTF with metallacarborane anions: (BPDT-TTF)[3,3 ′-Сr(1,2-C2B9H11)2] and (BPDT-TTF)[3,3′-Сo(1,2-C2B9H11)2] – Synthesis, structure, properties
Publication date: Available online 1 February 2018 Source:Journal of Organometallic Chemistry Author(s): Olga N. Kazheva, Denis M. Chudak, Gennady V. Shilov, Ekaterina A. Komissarova, Irina D. Kosenko, Andrey V. Kravchenko, Irina A. Shilova, Elena V. Shklyaeva, Georgy G. Abashev, Igor B. Sivaev, Vladimir A. Starodub, Lev I. Buravov, Vladimir I. Bregadze, Oleg A. Dyachenko The first molecular conductors based on bis(1,3-propylenedithio)tetrathiafulvalene and transition metal bis(dicarbollides) (BPDT-TTF)[3,3′-Сr (1,2-C2B9H11)2] (1) and (BPDT-TTF)[3,3′-Сo (1,2-C2B9H11)2] (2) were synthesized and their crystal ...
Source: Journal of Organometallic Chemistry - February 1, 2018 Category: Chemistry Source Type: research

Large-scale synthesis of novel sterically hindered acenaphthene-based α-diimine ligands and their application in coordination chemistry
Publication date: Available online 1 February 2018 Source:Journal of Organometallic Chemistry Author(s): Lihua Guo, Wenyu Kong, Yanjian Xu, Yuliang Yang, Rui Ma, Li Cong, Shengyu Dai, Zhe Liu An efficient method to synthesize novel highly sterically hindered acenaphthene-based α-diimine ligands bearing bulky diarylmethyl moiety was achieved by two-step reactions. These reactions could be carried out on a scale of 100 g with no chromatography involved. On the basis of this method, a series of novel highly sterically hindered acenaphthene-based α-diimine Pd(II) and Ni(II) complexes, imidazolium precursors and ...
Source: Journal of Organometallic Chemistry - February 1, 2018 Category: Chemistry Source Type: research

Copper(II) complexes of a heterotopic N-heterocyclic carbene ligand: Preparation and catalytic application
Publication date: Available online 1 February 2018 Source:Journal of Organometallic Chemistry Author(s): Shih-Chieh Aaron Lin, Yi-Hung Liu, Shie-Ming Peng, Shiuh-Tzung Liu Copper complexes containing a N-heterocylic carbene (NHC)/amidate/pyridine tridentate, 3-mesityl-1-(2-oxo-2-[{pyridin-2-ylmethyl}amino]ethyl)-imidazolin-2-ylidene (HL), were synthesized and characterized. By X-ray single crystal analysis, both Cu(L)(OAc) (3a) and Cu(L)Br (3b) show that the metal center is coordinated by a CNN-tridentate and a anionic donor in a slightly distorted square-planar geometry. These copper complexes are active as catalysts for...
Source: Journal of Organometallic Chemistry - February 1, 2018 Category: Chemistry Source Type: research

Recent aspects of the ten-vertex dicarbaborane chemistry
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Bohumil Štíbr A review on recent developments in the chemistry of ten-vertex dicarbaboranes is presented. This chemistry is essentially derived from that of the nido-5,6-C2B8H12 dicarbaborane, the most significant compound of the 10-vertex dicarbaborane series. This carborane gave rise to all the three closo-C2B8H10 isomers and to arachno-6,9-C2B8H14 that serve as substrates for various reactions outlined in this work. Individual chemical transformations are discussed within the context of possible reacti...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

(Indenyl)rhodacarboranes. Electronic versus steric effects on the conformation of cyclic ligands
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Mikhail A. Arsenov, Vladimir B. Kharitonov, Elizaveta R. Sovdagarova, Alexander F. Smol'yakov, Dmitry A. Loginov (Indenyl)rhodacarboranes 1,2-R2-3-(η5-indenyl)-3,1,2-RhC2B9H9 (2a: R = H; 2b: R = Me) and 3-(η5-indenyl)-4-SMe-3,1,2-RhC2B9H10 (3) were synthesized by reactions of the iodide complex [(η5-indenyl)RhI2]n (1b) with Tl[Tl(η-7,8-R2-7,8-C2B9H9)] or Tl[9-SMe2-7,8-C2B9H10]. The formation of 3 is accompanied by monodemethylation of the SMe2 substituent. The structures of rhodacarboranes 2b, 3...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Diferrocenyl(areno)oxazoles, spiro(arenooxazole)cyclopropenes, quinolines and areno[1,4-]oxazines: Synthesis, characterization and study of their antitumor activity
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Jessica J. Sánchez García, Marcos Flores-Álamo, Elena Martínez-Klimova, Teresa Ramírez Apan, Elena I. Klimova A novel 2-(Z,E-1,2-diferrocenylvinyl)arenooxazoles 4a-f and 5a-e (24–32%, 2:1, respectively), 3-ferrocenyl-2-ferrocenylmethyl-2-morpholino-2H-areno[1,4]oxazines 7a-f (22–33%), 2′,3′-diferrocenyl-3H-spiro[areno[d]oxazole-2,1′-cycloprop[2]ene] 6-f (5–6%), 2-ferrocenylarenooxazoles 3a-e (4–6%), and 3,4-diferrocenyl-8-hydroxyquinolines 8d-...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

N-[Chloro(dimethyl)silyl]methyl-N,N ′-diphenylurea: Synthesis and structure
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Nataliya F. Lazareva, Irina V. Sterkhova, Alexander I. Albanov N-[Chloro(dimethyl)silyl]methyl-N,N′-diphenylurea with intramolecular coordination bond C=O→Si was prepared by interaction of N,N′-diphenylurea with silane ClCH2SiMe2Cl. Structure of this compound was confirmed by 1H, 13C, 29Si NMR spectroscopy and X-ray diffraction analysis. Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Different reactivity of cyclooctadiene complexes 3,3-(cod)-8-SMe2-closo-3,1,2-RhC2B9H10 and 1,8-Me2-2,2-(cod)-11-SMe2-2,1,8-closo-RhC2B9H8 toward iodine
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Mikhail M. Vinogradov, Yulia V. Nelyubina, Nikolay S. Ikonnikov Reaction of the thallium salt Tl[7,8-Me2-10-SMe2-7,8-nido-C2B9H8] with [(cod)RhCl]2 in THF furnishes new rhodacarborane 1,2-Me2-3,3-(cod)-8-SMe2-3,1,2-closo-RhC2B9H8 (1). The latter undergoes 1,2 → 1,7 carbon atom isomerization upon reflux in o-xylene for 5 h producing complex 1,8-Me2-2,2-(cod)-11-SMe2-2,1,8-closo-RhC2B9H8 (2). Reaction of complex 2 with 1 equiv of I2 in benzene results in a loss of the cod ligand and formation of product 3, con...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Direct C-Li/C-H coupling of pentafluorophenyl lithium with azines - An atom- and step-economical strategy for the synthesis of polyfluoroaryl azaaromatics
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Mikhail V. Varaksin, Timofey D. Moseev, Valery N. Charushin, Oleg N. Chupakhin The SN H methodology has successfully been applied for the direct C(sp2)-H functionalization of azaaromatics through the C-Li/C-H coupling of pentafluorophenyl lithium with azines and their N-oxides. As a result, a number of novel fluorinated biheterocyclic ensembles, that are of interest in the design of bioactive molecules and advanced materials, have been prepared in good to excellent yields under rather mild condition. Graphical abstract...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Ferrocene-linked porous organic polymers for carbon dioxide and hydrogen sorption
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Xuejiao Sun, Yipeng Qi, Jianquan Li, Weiguo Wang, Qingyu Ma, Jianjun Liang Two novel ferrocene-containing microporous polymers, FPOP-1 and FPOP-2, have been prepared by Sonogashira-Hagihara coupling reactions of 1,1′-diethynylferrocene with tri (4-bromophenyl)phenylsilane or tetrakis (4-bromophenyl)silane. The resultant polymers show high thermal stability and high porosity with Brunauer-Emmer-Teller (BET) surface area of up to 954 m2 g−1 (FPOP-2) and total pore volume of up to 0.74 cm3 g−1 (F...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

The cytochrome b6f complex: DFT modeling of the first step of plastoquinol oxidation by the iron-sulfur protein
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Leila Y. Ustynyuk, Alexander N. Tikhonov In chloroplasts, the cytochrome (Cyt) b 6 f complex (plastoquinol-plastocyanin-oxidoreductase) provides connectivity between photosystems (PS) II and I, oxidizing plastoquinol (PQH2) formed in PSII and reducing plastocyanin (electron donor to PSI). The overall rate of the intersystem electron transport is determined by PQH2 oxidation by the Cyt b 6 f complex. In this work, using the DFT method, we have modeled the first step of PQH2 oxidation by the iron-sulfur protein (ISP) of ...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Influence of highly basic phosphine ligand on the reactivity and hydrolysis of P4 and P4S3 supported by ruthenium fragments
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Maria Caporali, Fuencisla Delgado Calvo, Carla Bazzicalupi, Stefano Seniori Costantini, Maurizio Peruzzini Substitution of PPh3 in [RuCp(PPh3)2Cl] with highly basic PMe3 gave a remarkable change in the reactivity towards P4 and unexpectedly only the bimetallic complex cation [{RuCp(PMe3)2}2(μ,η1:1-P4)]2+ (3) was formed which was characterized by NMR spectroscopy and single crystal X-ray diffraction analysis. The equimolar reaction between the synthon [RuCp(PMe3)2]+ and the mixed cage P4S3 is highly selective qua...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Computational studies on Ni-catalyzed C −O bond activation of esters
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Xin Li, Xin Hong Ni-catalyzed C−O bond activation of esters provides an unprecedented synthetic approach to utilize esters. To understand the mechanistic details of the Ni-catalyzed C−O bond activation, computational chemists have dedicated remarkable efforts to elucidate the origins of reactivities and selectivities of this important process. In order to provide a general perspective of this exciting area, this review summarizes the recent advances of the computational studies involving Ni-catalyzed C&minu...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Carbamato-benzylidene ruthenium chelates – Synthesis, structure and catalytic activity in olefin metathesis
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Szymon Rogalski, Patrycja Żak, Piotr Pawluć, Maciej Kubicki, Cezary Pietraszuk New carbamato-κN-benzylidene ruthenium chelates were synthesized from the first [RuCl2(PCy3)2(=CHPh)] and second [RuCl2(SIMes)(PCy3)(=CHPh)] generation Grubbs catalysts by metathetic exchange of benzylidene ligand for tert-butyl (2-vinylphenyl)carbamates bearing benzylidene ligand substituted in the position para to carbamato functionality with methyl or trifluoromethyl group. In all metathetical transformations tested, i.e. in ROMP ...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Direct energetic evaluation of aromaticity by cleaving the rings of cyclic compounds
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Ke An, Jun Zhu Aromaticity, one of the central topics in chemistry, has attracted continuing interest of both experimentalists and theoreticians. Given that the original definition of aromaticity could be derived from the fact that the cyclic aromatic species are thermodynamically more stable than the corresponding acyclic conjugated ones, here we propose a direct evaluation of the aromatic stabilization energy (ASE) by following this definition to compute the energy difference between the cyclic compound and its corre...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Synthesis and characterization of novel positively charged organocobaloximes as catalysts for the fixation of CO2 to cyclic carbonates
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Ahmet Kilic, Mustafa Durgun, Emine Aytar, Rahime Yavuz A series of cobaloxime complexes (1-6) and corresponding to positively charged phosphonium linked cobaloximes (called cobaloximes-PCPL) (1a-6a) have been prepared in high yields and characterized by means of NMR (1H, 13C, and 31P) spectra, FT-IR spectra, UV-Vis spectra, mass spectra, melting point as well as elemental analysis. Following a full characterization, the study of spectroscopic properties of these novels cobaloximes/cobaloximes-PCPL compounds was done in...
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

Synthesis of ferrocene indanone derivatives via trinuclear N-heterocyclic carbene palladium(II)-catalyzed cyclocarbonylation of o-bromoarylferrocene
Publication date: Available online 31 January 2018 Source:Journal of Organometallic Chemistry Author(s): Tao Wang, Renjie Wang, Wanli Wang, An'an Zhang, Lantao Liu A new route to ferrocene indanone derivatives has been developed via the trinuclear N-heterocyclic carbene palladium(II)-catalyzed carbonylative C-C bond formation. Under a CO atmosphere, using o-bromoarylferrocene as substrate, this reaction proceeded smoothly to give the desired products in moderate to excellent yields within hours. Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - January 31, 2018 Category: Chemistry Source Type: research

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