Functionalized nitrogen ligands (CN) for palladium catalyzed cross-coupling reactions (part II)
Publication date: Available online 3 October 2018Source: Journal of Organometallic ChemistryAuthor(s): Arjun KumbharAbstractIn recent years, considerable effort has been focused in Pd catalyzed cross-coupling reactions, especially the use of less reactive and economically viable substrates like aryl chlorides. Unfortunately, Pd complexes containing the ligands having only N as a donor atom has some limitations, as it couples, mostly aryl iodides and bromides with different nucleophiles, and shows less activity towards aryl chlorides. This restriction can overwhelm by the use of Pd complexes containing N in combination with...
Source: Journal of Organometallic Chemistry - October 5, 2018 Category: Chemistry Source Type: research

Synthesis, characterization and reactions of [RhCl(CO){(Ph2P(CH2CH2O)mCH2CH2Ph2-P,P’)}]n (m = 3, 4, 5 n = 1, 2 …) metallacrown crown ethers
Publication date: 1 December 2018Source: Journal of Organometallic Chemistry, Volume 876Author(s): Dale C. Smith, Ethan C. Cagle, Gary M. GrayAbstractThe reactions of [RhCl(cod)]2 and Ph2P(CH2CH2O)nCH2CH2PPh2P (n = 3, 4, 5) under a CO atmosphere yield [RhCl(CO){(Ph2P(CH2CH2O)n CH2CH2Ph2-P,P′)}]m monocarbonyl metallacrown ethers. These complexes are mixtures of cyclic n-mers and monomers with trans coordination geometries at the rhodium. The monocarbonyl rhodium metallacrown ethers reversibly react with CO at atmospheric pressure to form [RhCl(CO)2{(Ph2P(CH2CH2O)nCH2CH2Ph2-P,P′)}]m dicarbonyl metallacrown et...
Source: Journal of Organometallic Chemistry - October 5, 2018 Category: Chemistry Source Type: research

Synthesis, photo- and electro-luminescence of dinuclear Ir(III) complexes containing bis-β-diketonate carbazole ligand
Publication date: 15 December 2018Source: Journal of Organometallic Chemistry, Volume 877Author(s): Yuling Zhao, Yanmei Li, Tianzhi Yu, Xinyu Li, Xiaoxiao Liu, Youjia Wang, Hui ZhangAbstractA carbazole-functionalized bis-β-diketone as ancillary ligand, 1,1'-(9-(heptan-3-yl)-9H-carbazole-3,6-diyl)bis(4,4,4-trifluorobutane-1,3-dione) (H2L), which contains two trifluorinated alkyl groups, has been prepared for the synthesis of two green and red emitting dinuclear Ir(III) complexes with the general formula Ir2(CˆN)4L [CˆN = 3-(pyridine-2-yl)coumarinato (1L) and 2-(1-naphthyl)benzothiazole (2L)]. The photophy...
Source: Journal of Organometallic Chemistry - October 5, 2018 Category: Chemistry Source Type: research

A new class of organocobaloximes based FeNi3/DFNS for reduction of 4-nitrophenol and 2-nitroaniline
This study investigated the potential application of an efficient, easily recoverable, and reusable dendritic fibrous nanosilica (DFNS) magnetic nanoparticle catalyst, which supported cobaloxime complexes and corresponding to positively charged phosphonium linked cobaloximes (FeNi3/DFNS/Cobaloxime/PCPL MNPs) for catalytic reduction of 4-NP and 2-NA. FeNi3/DFNS/Cobaloxime/PCPL MNPs were thoroughly characterized by using TEM, FE-SEM, VSM, TGA, ICP-MS, and BET. Analysis of the recycled catalyst by ICP-MS showed only minor modifications in its morphology after the reaction and thus confirmed the strength of the catalyst.Graphi...
Source: Journal of Organometallic Chemistry - October 5, 2018 Category: Chemistry Source Type: research

Synthesis and architecture of polystyrene-supported Schiff base-palladium complex: Catalytic features and functions in diaryl urea preparation in conjunction with Suzuki-Miyaura cross-coupling reaction by reductive carbonylation
Publication date: Available online 21 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Priyanka Basu, Sk Riyajuddin, Tusar Kanto Dey, Aniruddha Ghosh, Kaushik Ghosh, Sk Manirul IslamAbstractThis work represents an efficient and unique phosphine-free approach for the polystyrene embedded Schiff-base palladium catalyzed diaryl urea synthesis and Suzuki-Miyaura cross-coupling reaction by reductive carbonylation process. The careful instrumental investigations with FE-SEM, EDAX, TGA, UV–Vis, FTIR, AAS, and elemental analysis precisely characterized the developed heterogeneous catalyst. Reaction paramet...
Source: Journal of Organometallic Chemistry - September 22, 2018 Category: Chemistry Source Type: research

Mechanistic insight into the Rh-catalyzed mono- and double-decarbonylation of 1,4-diphenylbut-3-yne-1,2-dione: A computational study
Publication date: Available online 21 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Fanmei Kong, Hui SunAbstractThe reaction mechanisms on the Rh-catalyzed mono- and double-decarbonylation of 1,4-diphenylbut-3-yne-1,2-dione (R) have been computationally investigated by employing density functional theory (DFT) calculations. In reaction A, by using Xantphos as ligand and ethylbenzene as solvent, R could afford monodecarbonylated product (P1) firstly and then transform into doubledecarbonylation ynone (P2) irreversibly, so P2 is the major product. In contrast, in reaction B (by employing dppe as ligand ...
Source: Journal of Organometallic Chemistry - September 22, 2018 Category: Chemistry Source Type: research

Rhenium-catalyzed α-alkylation of enol acetates with alcohols or ethers
Publication date: Available online 20 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Rui Umeda, Yuuki Takahashi, Takaaki Yamamoto, Hideki Iseki, Issey Osaka, Yutaka NishiyamaAbstractWhen alcohols were treated with enol acetate in the presence of a catalytic amount of a rhenium complex, ReBr(CO)5, the carbon-carbon bond formation of the alcohols and enol acetate smoothly proceeded to give the corresponding ketones and aldehyde in moderate to good yields. For the reaction of allylic alcohols, γ,δ-unsaturated carbonyl compounds were obtained in good yields. When ethers were used instead of alc...
Source: Journal of Organometallic Chemistry - September 21, 2018 Category: Chemistry Source Type: research

The role of Si in Ir(SiNN) catalyst and chemoselectivity of dehydrogenative borylation over hydroborylation: A theoretical study
Publication date: Available online 20 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Shuang Chen, Shao-Fei Ni, Pei-Nian Liu, Li DangAbstractAn Ir(SiNN) complex has been reported that efficiently catalyzes dehydrogenative C-H borylation, rather than hydroborylation, of terminal alkynes. Here we performed density functional theory calculations to elucidate the reaction mechanism and attempt to explain the strict chemoselectivity for dehydrogenative borylation. The calculations suggest that the chemoselectivity arises mainly from (1) interaction between Si and the metal hydride, which stabilizes the metal...
Source: Journal of Organometallic Chemistry - September 21, 2018 Category: Chemistry Source Type: research

Synthesis, characterization, and olefin (co)polymerization behavior of unsymmetrical α-diimine palladium complexes containing bulky substituents at 4-position of aniline moieties
Publication date: Available online 20 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Lihua Guo, Yanlan Liu, Wenting Sun, Qing Du, Yuliang Yang, Wenyu Kong, Zhe Liu, Darui ChenAbstractThree novel unsymmetrical α-diimine Pd(II) complexes containing bulky substituents at 4-position of aniline moieties were prepared and characterized. Unfortunately, the introduction of large substituents on para- N-aryl moieties did not slow the exchange between the anti and syn forms for these complexes. These unsymmetrical α-diimine Pd(II) complexes also did not improve thermal stability and broaden molecular...
Source: Journal of Organometallic Chemistry - September 21, 2018 Category: Chemistry Source Type: research

Synthesis of gold organometallics at the nanoscale
We report the synthesis of aryldiazonium tetrachloroaurate(III) salts [X-4-C6H4N≡N]AuCl4 (X = F, Cl, Br, I, CN, NO2) and their mild reduction to covalently functionalized nanoparticles. The synthesis of the salts was carried out by the oxidation of anilines, dissolved in HCl, using sodium nitrite followed by the exchange of the counter anion with [AuCl4]- in water. In another procedure, the anilines were protonated with H[AuCl4] in acetonitrile followed by one-electron oxidation using nitrosonium salt [NO]X (X = BF4−, PF6−). Raman and ATR-FTIR spectroscopy displayed the diazonium νN≡N and...
Source: Journal of Organometallic Chemistry - September 21, 2018 Category: Chemistry Source Type: research

Novel titanium (IV) complexes with 1,2-diolate ligands: Synthesis, structure and catalytic activities in ultra-high molecular weight polyethylene production
Publication date: Available online 21 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Vladislav A. Tuskaev, Svetlana Ch Gagieva, Dmitrii A. Kurmaev, Victor N. Khrustalev, Pavel V. Dorovatovskii, Elena S. Mikhaylik, Evgenii K. Golubev, Mikhail I. Buzin, Sergey V. Zubkevich, Nikolay A. Kolosov, Galina G. Nikiforova, Viktor G. Vasil'ev, Boris M. BulychevAbstractA series of titanium (IV) complexes 3a-f stabilized by 1,2-diolate ligands 2 a-e have been synthesized. Structures of complexes 3d and 3e have been determined by X-ray diffraction. Titanium atoms in these complexes have a distorted square-pyramidal ...
Source: Journal of Organometallic Chemistry - September 21, 2018 Category: Chemistry Source Type: research

Orange red iridium complexes with good electron mobility and mild OLED efficiency roll-off
Publication date: Available online 19 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Yong-Hui Zhou, Dong Jiang, You-Xuan ZhengAbstractTwo iridium(III) complexes with 1-(3,5-bis(trifluoromethyl) pyridin-4-yl)isoquinoline (tntpiq) as main ligand, 2-(5-pyridin-4-yl)-1,3,4-oxadiazol-2-yl)phenol (pop) and 2-(5-pyridin-4-yl)-1,3,4-thiadiazol-2-yl)phenol (psp) as ancillary ligands were investigated. Both complexes emit orange red lights with different photoluminescence efficiencies (Ir(tntpiq)2(pop): λem = 585 nm, Φ = 0.41 and Ir(tntpiq)2(psp): λem = 590 nm, Φ = 0.59)...
Source: Journal of Organometallic Chemistry - September 20, 2018 Category: Chemistry Source Type: research

Photoluminescence and electroluminescence of four orange-red and red organic iridium(III) complexes
Publication date: Available online 19 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Ning Su, You-Xuan ZhengAbstractUsing 1-(4-(trifluoromethyl)phenyl)isoquinoline (tfmpiq) and 4-(4-(trifluoromethyl)phenyl) quinazoline (tfmpqz) as the main ligands and pyrazole pyridine derivatives (mepzpy: 2-(3-methyl-1H-pyrazol-5-yl)pyridine, cf3pzpy: 2-(3-(trifluoromethyl)- 1H-pyrazol-5-yl)pyridine) as the ancillary ligands, four iridium(III) complexes (PIQ-Ir1-me, PIQ-Ir2-cf3, PQZ-Ir3-me and PQZ-Ir4-cf3) were synthesized and investigated. Due to the variation of the ligands, these Ir(III) complexes showed different ...
Source: Journal of Organometallic Chemistry - September 20, 2018 Category: Chemistry Source Type: research

Efficient indenones synthesis via iridium-catalyzed decarboxylative annulation between 2-oxo-2-phenylacetic acids and alkynes
Publication date: Available online 20 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Xiaobo Yu, Shudong Geng, Guanchen Liu, Weijie Guo, Jianhui WangAbstractEfficient iridium-catalyzed decarboxylative annulation reactions between 2-oxo-2-phenylacetic acids and alkyne derivatives has been achieved. [IrCp*Cl2]2 with a (CH3OC6H4)3P ligand, AgSbF6 and Cu(OAc)2 additives was the most efficient catalytic system for this transformation. This reaction is suitable for a broad range of alkynes and 2-oxo-2-phenylacetic acids and a variety of indenone derivatives were obtained in medium to high yields. This work pr...
Source: Journal of Organometallic Chemistry - September 20, 2018 Category: Chemistry Source Type: research

Mechanistic insight into the Rh(III)-catalyzed cascade annulation of ο-ethynylanilines with diazo compounds towards Benzo[a]carbazoles
Publication date: Available online 18 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Weirong Wu, Hua Hou, Baoshan WangAbstractA mechanistic analysis for the reactions of RhIII-catalyzed intermolecular cascade annulation of o-ethynylanilines with diazo compounds has been performed in details using density functional theory (DFT) calculations. It is revealed theoretically that the reaction mechanisms starting from intermediate 6 disagree with those proposed by the experimenters. The rate-determining step of the catalytic cycle is the dinitrogen elimination process with an overall barrier of 31.1 kcal...
Source: Journal of Organometallic Chemistry - September 18, 2018 Category: Chemistry Source Type: research

Asymmetric transfer hydrogenation of acetophenone derivatives using 2-benzyl-tethered ruthenium (II)/TsDPEN complexes bearing η6-(p-OR) (R = H, iPr, Bn, Ph) ligands
We report the preliminary asymmetric transfer hydrogenation (ATH) results on a range of primarily acetophenone derivatives with these new complexes using FA/TEA (5:2) as a reducing agent; the results confirm that these catalysts are capable of reducing the substrates within 48 h with excellent enantioselectivities.Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - September 18, 2018 Category: Chemistry Source Type: research

Alkylation versus trans-silylation of N-methyl-N-trimethylsilylacetamide with ambident electrophiles (chloromethyl)fluorosilanes
Publication date: Available online 15 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Nataliya F. Lazareva, Nina N. Chipanina, Larisa P. Oznobikhina, Bagrat A. ShainyanAbstractBifunctional silanes ClCH2SiF3 and ClCH2SiF2Me react with N-trimethylsilyl-N-methylacetamide 1a and its tautomer О-trimethylsilyl-N-methylacetimidate 1b as ambident substrates to give the products of trans-silylation N-{[chloro(difluoro)silyl]methyl}N-methylacetamide 11a and N-{[chloro(fluoro)methylsilyl]methyl}N-methylacetamide 12a with liberation of Me3SiF, as well as the products of alkylation N-methyl-N-[(trifluorosilyl)methy...
Source: Journal of Organometallic Chemistry - September 17, 2018 Category: Chemistry Source Type: research

New dioxido-vanadium(V) complexes containing hydrazone ligands: Syntheses, crystal structure and their catalytic application toward CH bond functionalization
Publication date: Available online 13 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Sunshine D. Kurbah, M. Asthana, Ibanphylla Syiemlieh, Alzelia A. Lywait, M. Longchar, R.A. LalAbstractNew dioxido-vanadium(V) complexes derived from hydrazone ligands have been synthesized in good yield. The complexes were characterized by elemental analysis, IR, UV–Visible and 1H NMR spectroscopies. The structure of both the complexes was established by Single Crystal X-ray crystallography. Complex 1 crystallized in monoclinic P21/n space group, with cell parameters a = 8.3725(5) Å, b = 15.0475(17)...
Source: Journal of Organometallic Chemistry - September 13, 2018 Category: Chemistry Source Type: research

Editorial Board
Publication date: 1 November 2018Source: Journal of Organometallic Chemistry, Volume 874Author(s): (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - September 13, 2018 Category: Chemistry Source Type: research

Graphical abstract TOC
Publication date: 1 November 2018Source: Journal of Organometallic Chemistry, Volume 874Author(s): (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - September 13, 2018 Category: Chemistry Source Type: research

Highly regio- and Stereoselective Diels–Alder Cycloadditions of α-Alkoxyvinyl(ethoxy)carbene complexes with exo-heterocyclic dienes
Publication date: Available online 7 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Alberto Feliciano, M. Inés Flores-Conde, Rosa Padilla, Carlos Espinoza-Hicks, Alejandro Camacho-Dávila, Marvin Rentería, Miguel Angel Vázquez, Joaquín Tamariz, Francisco DelgadoAbstractA comparative study of reactivity and selectivity was carried out between the α-alkoxyvinyl(ethoxy)carbene complexes of group 6 metals (CO)5M = C[C(=CH2)(OR)]OEt [1a–c: M = Cr; 6a–c: M = Mo; 7a–c: M = W; a, R = Et; b, R = n–Pr; c, R = n–Bu] ...
Source: Journal of Organometallic Chemistry - September 7, 2018 Category: Chemistry Source Type: research

Aluminum Complexes Based on Tridentate Amidoalkoxide NNO-Ligands: Synthesis, Structure, and Properties
Publication date: 15 November 2018Source: Journal of Organometallic Chemistry, Volume 875Author(s): Kirill V. Zaitsev, Valeriy S. Cherepakhin, Alexander Zherebker, Alexey Kononikhin, Eugene Nikolaev, Andrei V. ChurakovAbstractA series of novel NNO-type ligands 12a-17a, LH2, R1N(CH2CH2NHTs)CHR2CR3R4OH (R1 = Bn, R3 = R4 = H; R2 = H (12a), R2= (S)-Ph (13a), R2= (S)-Bn (14a), R2= (S)-i-Bu (15a); R1 = R2= (R)-Me, R3 = H, R4= (S)-Ph (16a); R1 = Bn, R2= (S)-i-Bu, R3 = R4 = Ph (17a)) was obtained; the ligands LH2 feature various degree of substitution, steric bulkiness, and chirality. Treatment ...
Source: Journal of Organometallic Chemistry - September 7, 2018 Category: Chemistry Source Type: research

Tetraphenylcyclopentadienyl rhodium complexes in stoichiometric and catalytic CH functionalization
Publication date: Available online 4 September 2018Source: Journal of Organometallic ChemistryAuthor(s): David L. Davies, Charles E. Ellul, Kuldip SinghAbstractThe use of [RhCl2(η-C5Ph4H)]2 for stoichiometric and catalytic CH functionalization has been evaluated. For the substrates studied, CH activation, alkyne insertion and CN reductive elimination are all possible at room temperature, similar to corresponding reactions with [RhCl2(η-C5Me5)]2. The tetraphenylcyclopentadienyl ligand shows promise for controlling regioselectivity in catalytic CH functionalization.Graphical abstract[RhCl2(η-C5Ph4H)]2 undergoes s...
Source: Journal of Organometallic Chemistry - September 6, 2018 Category: Chemistry Source Type: research

Synthesis, characterization and reactions of [RhCl(CO){(PPh2P(CH2CH2O)mCH2CH2Ph2P,P′)}]n (m = 3, 4, 5 n = 1, 2 …) metallacrown crown ethers
Publication date: Available online 4 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Dale C. Smith, Ethan Cagle, Gary M. GrayAbstractThe reactions of [RhCl(cod)]2 and Ph2P(CH2CH2O)nCH2CH2PPh2P (n = 3, 4, 5) under a CO atmosphere yield [RhCl(CO){(Ph2P(CH2CH2O)n CH2CH2Ph2-P,P′)}]m monocarbonyl metallacrown ethers. These complexes are mixtures of cyclic n-mers and monomers with trans coordination geometries at the rhodium. The monocarbonyl rhodium metallacrown ethers reversibly react with CO at atmospheric pressure to form [RhCl(CO)2{(Ph2P(CH2CH2O)nCH2CH2Ph2-P,P′)}]m dicarbonyl metallacrown...
Source: Journal of Organometallic Chemistry - September 6, 2018 Category: Chemistry Source Type: research

Enantioselective catalytic hydrosilylation of propiophenone with a simple combination of a cationic iridium complex and a chiral azolium salt
This study aims to propose a simple procedure for the development of enantioselective hydrosilylation of a ketone using catalytic amounts of [Ir(cod)2]BF4 and chiral azolium salt. Previously, catalytic asymmetric hydrosilylation reactions have used well-defined metal-N-heterocyclic carbene (NHC) complexes. The proposed method offers an important advantage of avoiding preparation of NHC-metal species. Several reaction parameters including the amount of reductant, solvent, catalyst loading, and ligand structure were evaluated. In addition, the investigation of the reaction progress as a function of time revealed that an irid...
Source: Journal of Organometallic Chemistry - September 6, 2018 Category: Chemistry Source Type: research

A highly efficient heterogeneous palladium-catalyzed carbonylative annulation of 2-aminobenzamides with aryl iodides leading to quinazolinones
Publication date: Available online 4 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Shengyong You, Bin Huang, Tao Yan, Mingzhong CaiAbstractThe first heterogeneous carbonylative annulation of 2-aminobenzamides with aryl iodides was achieved in N,N-dimethylformamide (DMF) at 120 °C under 10 bar of carbon monoxide by using an MCM-41-immobilized bidentate phosphine palla-dium(II) complex [MCM-41-2P-Pd(OAc)2] as catalyst and 1,8-diazabicycloundec-7- ene (DBU) as base, yielding a wide variety of quinazolinone derivatives in good to excellent yields. The new heterogeneous palladium catalyst can easil...
Source: Journal of Organometallic Chemistry - September 6, 2018 Category: Chemistry Source Type: research

Ionic η5-Cp-Ruthenium (II) complexes as potential anticancer agents
Publication date: Available online 4 September 2018Source: Journal of Organometallic ChemistryAuthor(s): André Delavault, Frank R. Fronczek, Wu Xu, Radhey S. SrivastavaAbstractIonic organometallic ruthenium(II) complexes, [η5-CpRu(PPh3) (1,10-phenanthroline)]+Cl−1, [η5-CpRu(PPh3) (4,7-dimethyl, 1,10-phenanthroline)]+Cl−2, and [η5-CpRu(PPh3) (1,10-phenanthroline-5-amine)]+Cl−3 have been synthesized and characterized. The molecular structures of the complexes 1 and 2 were confirmed by single-crystal X-ray structure analysis. Cytotoxicity assays demonstrated that these compounds show signi...
Source: Journal of Organometallic Chemistry - September 6, 2018 Category: Chemistry Source Type: research

Ligand-free scandium alkyl and alkoxide complexes for immortal ring-opening polymerization of lactide
Publication date: Available online 3 September 2018Source: Journal of Organometallic ChemistryAuthor(s): Hongyan Xie, Chunji Wu, Dongmei Cui, Yang WangAbstractLigand-free Ln (CH2SiMe3)3 (THF)2 (1: Ln = Sc; 2: Ln = Lu; 3: Ln = Er; 4: Ln = Y) and La(CH2C6H4-o-NMe2)3 (5) are employed as the initiators for ring-opening polymerization (ROP) of rac-lactide (rac-LA). Complex 4 solely is active but uncontrolled, while complex 1 is inert. In presence of excess benzhydrol, complexes 1–5 can promote the ROP of LA smoothly, in which the molecular weight distribution values of the resultant polymer are related to ...
Source: Journal of Organometallic Chemistry - September 5, 2018 Category: Chemistry Source Type: research

Mechanistic insight into the ruthenium-catalyzed cycloaddition of enynes with alkynes: A theoretical study
Publication date: Available online 31 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Ruiqiu Liu, Yunfei Tie, Xiaoyan Zhao, Jinjiao Zhu, Jie Zou, Tao LiuAbstractThe density functional theory (DFT) has been employed to elucidate the mechanisms of ruthenium-catalyzed cycloaddition of enynes with alkynes. The calculated results suggest that there are similar reaction pathways for symmetrical and nonsymmetrical alkynes, including oxidative cyclization, insertion of the alkynes, and reductive elimination, respectively. The oxidative cyclization is calculated to be the rate-determining step. The regioselectivity...
Source: Journal of Organometallic Chemistry - September 1, 2018 Category: Chemistry Source Type: research

Sandwich complexes of iron and ruthenium with the semiconducting aromatic hydrocarbon picene
Publication date: Available online 31 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Andrei M. Shved, Yulia V. Nelyubina, Dmitry S. PerekalinAbstractPentacyclic aromatic hydrocarbon picene C22H14 was synthesized by the improved two-step procedure from 1-naphthaldehyde in ca. 50% total yield. Reaction of picene with ferrocene in the presence of AlCl3 produced the binuclear iron complex [(CpFe)2(C22H14)](PF6)2. Reactions of picene with [Cp*Ru(MeCN)3]PF6 produced mono- or binuclear complexes depending on the concentration and ratio of reactants. The structures of the binuclear iron complex and the mononuclea...
Source: Journal of Organometallic Chemistry - September 1, 2018 Category: Chemistry Source Type: research

Synthesis and characterization of selenium(I/II) and tellurium(IV) derivatives of amino acids
Publication date: Available online 30 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Puspendra Singh, Harkesh B. Singh, Ray J. ButcherAbstractThe direct reaction between Te metal and methyl 2-(2-bromoacetamido)propanoate (27) at room temperature, yields the first exapmple of organotellurium(IV) derivative (MeOC(O)CH(Me)NHCOCH2)2TeBr2 (31). Similarly, reaction of Te with methyl 2-(2-bromoacetamido)acetate (26) and methyl 2-(2-bromoacetamido)-3-phenylpropanoate (28) in presence of NaI in acetone gives MeOC(O)CH2NHCOCH2I (29), MeOC(O)CH(R)NHCOCH2)2TeI2 (R = H (30) and CH2Ph (32). Treatment of 26/27/28 wi...
Source: Journal of Organometallic Chemistry - September 1, 2018 Category: Chemistry Source Type: research

Synthesis, structure, and reactivity of doubly trans-spanning bis(dialkyl selenide) complexes; a new route to diselenamacrocycles via alkene metathesis in metal coordination spheres
Publication date: Available online 31 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Hemant Joshi, Sugam Kharel, Nattamai Bhuvanesh, John A. GladyszAbstractThe reaction of selenium with NaBH4 and Br(CH2)6CH = CH2 (2.0 equiv each) gives the dialkyl selenide Se((CH2)6CH = CH2)2 (91% after workup) which is combined with PtCl2 (0.5 equiv, toluene) to give trans-PtCl2(Se((CH2)6CH = CH2)2)2 (10, 85%). The reaction of 10 and Grubbs' first generation catalyst yields macrocyclic trans-PtCl2(Se((CH2)6CH = CH(CH2)6)2Se) (11, 60%) as a mixture of syn/anti isomers with respect to the selenium lone pair...
Source: Journal of Organometallic Chemistry - September 1, 2018 Category: Chemistry Source Type: research

Aluminum complexes based on NNO-Ligands
Publication date: Available online 29 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Kirill V. Zaitsev, Valeriy S. Cherepakhin, Alexander Zherebker, Alexey Kononikhin, Eugene Nikolaev, Andrei V. ChurakovAbstractA series of novel NNO-type ligands 12a-17a, LH2, R1N(CH2CH2NHTs)CHR2CR3R4OH (R1 = Bn, R3 = R4 = H; R2 = H (12a), R2= (S)-Ph (13a), R2= (S)-Bn (14a), R2= (S)-i-Bu (15a); R1 = R2= (R)-Me, R3 = H, R4= (S)-Ph (16a); R1 = Bn, R2= (S)-i-Bu, R3 = R4 = Ph (17a)) was obtained; the ligands LH2 feature various degree of substitution, steric bulkiness, and chirality. Treatme...
Source: Journal of Organometallic Chemistry - August 30, 2018 Category: Chemistry Source Type: research

Synthesis of the labile rhenium(I) complexes fac-Re(CO)3(L)[κ2-O,O-FcC(O)CHC(O)Me] (where Fc = ferrocenyl; L = THF, H2O, alkyne) and alkyne addition to the diketonate ligand
Publication date: 1 November 2018Source: Journal of Organometallic Chemistry, Volume 874Author(s): Silvia Atim, Li Yang, Volodymyr Nesterov, Xiaoping Wang, Michael G. RichmondAbstractRefluxing equimolar amounts of 1-ferrocenyl-1,3-butanedione (Fcacac) with BrRe(CO)5 in THF yielded the labile solvent complex fac-Re(CO)3 (THF)[κ2-O,O-FcC(O)CHC(O)Me] (1) in 80% isolated yield. 1 may also be prepared in quantitative yield using fac-BrRe(THF)2(CO)3 as the starting rhenium complex. The THF molecule in 1 is replaced by H2O during chromatographic purification to furnish the corresponding aqua complex fac-Re(CO)3(H2O)[κ...
Source: Journal of Organometallic Chemistry - August 30, 2018 Category: Chemistry Source Type: research

Building blocks for oligomeric siloxanes –selective chlorination of hydrido-siloxanes
Publication date: Available online 29 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Thomas Hafner, Ana Torvisco, Frank UhligAbstractA new method was developed to achieve highly selective monochlorination of α,ω-dihydridosiloxanes, ((H)Me2SiO-(SiMe2O)n-SiMe2(H), n = 0–2; (H)R2SiO-SiR2(H); R = Me, iPr, Ph; 3,5-dihydridooctamethyltetrasiloxane, Me3SiO-(Si(H)MeO)2SiMe3) with trichloroisocyanuric acid (TCCA). The dependence of the selectivity of the monochlorination on the siloxane chain length is also discussed.Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - August 30, 2018 Category: Chemistry Source Type: research

Magnetic Cu0@HAP@γ-Fe2O3 nanoparticles: An efficient catalyst for one-pot three-component reaction for the synthesis of imidazo[1,2-a]pyridines
Publication date: 15 October 2018Source: Journal of Organometallic Chemistry, Volume 873Author(s): Wei Sun, Wei Jiang, Gan Zhu, Yiqun LiAbstractCu(0) incorporated magnetic hydroxyapatite nanoparticles (Cu0@HAP@γ-Fe2O3 NPs) was conveniently synthesized via the ion exchange reaction, oxidation, and reduction steps. The structure and composition of the nanohybrid were confirmed by FT-IR, SEM, EDS, TEM, XPS, and TGA. The magnetic Cu0@HAP@γ-Fe2O3 hybrid can efficiently catalyzed a one-pot multicomponent synthesis of imidazo[1,2-a]pyridine derivatives from 2-aminopyridine, aldehydes or glyoxylic acids, and alkynes or...
Source: Journal of Organometallic Chemistry - August 30, 2018 Category: Chemistry Source Type: research

Cyclometalation and pentafluorophenyl transfer in protonolysis of a chelating Bis-NHC Platinum(II) complex
Publication date: Available online 27 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Sirous Jamali, Soosan Hosseinmardi, Mehrafshan G. Jafari, Hamidreza SamoueiAbstractThe reactions of the bis-NHC platinum complex cis-[PtMe2(bisNHC1)], 1, in which bisNHC1 = 1,1′-methylene-3,3′-bis[(N-(tert-butyl)imidazole-2-ylidene], with strong acids and thermolysis of the reaction products were investigated. The reaction of 1 with 1 equiv B(C6F5)3 in acetone gave the borate complex cis-PtMe(bisNHC1)[OHB(C6F5)3], 2, that undergoes CH bond activation of one of the tBu wingtips at 50 °C and yields the...
Source: Journal of Organometallic Chemistry - August 29, 2018 Category: Chemistry Source Type: research

1,2 addition or cycloaddition of allenes by a dihafnium μ−Nitrido complex? A DFT study
Publication date: Available online 27 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Pengjie Li, Longfei Li, Xin Yue, Qianyue Wang, Min Pu, Zuoyin Yang, Ming LeiAbstractThe reaction mechanisms of the hydrogenation of [(η5-C5H2-1,2,4-Me3)2Hf]2(NCO) (μ2-N) (1) were studied using density functional theory (DFT) method. The calculated results indicate that the first step is the addition of H2 to the HfN double bond, the second step is the insertion of isocyanate into the bridging metal hydride. The metal centers with a low electronegativity benefits the hydrogenation of 1. Then the reaction mechanisms ...
Source: Journal of Organometallic Chemistry - August 29, 2018 Category: Chemistry Source Type: research

Asymmetric transfer hydrogenation of acetophenone derivatives using 2-benzyl-tethered ruthenium (II)/TsDPEN complexes bearing η6-(p-OR) (R = H, iPr, Bn, Ph) ligands
We report the preliminary asymmetric transfer hydrogenation (ATH) results on a range of primarily acetophenone derivatives with these new complexes using FA/TEA (5:2) as a reducing agent; the results confirm that these catalysts are capable of reducing the substrates within 48 h with excellent enantioselectivities.Graphical abstract (Source: Journal of Organometallic Chemistry)
Source: Journal of Organometallic Chemistry - August 29, 2018 Category: Chemistry Source Type: research

Efficient and selective aldehyde cyanosilylation catalyzed by Mg-Li bimetallic complex
Publication date: Available online 24 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Jia Li, Ting Yu, Man Luo, Qian Xiao, Weiwei Yao, Li Xu, Mengtao MaAbstractA NCN-pincer ligand-based Mg-Li bimetallic complex [NCN-MgBr2][Li(THF)4] 1 has been employed as an efficient catalyst for cyanosilylation of a wide range of aldehydes with trimethylsilyl cyanide (TMSCN) at room temperature in CDCl3. In addition, catalyst 1 shows a good tolerance towards various functional groups such as amide, acid, ester, heterocyclic and alkene etc. The chemoselective cyanosilylation of aldehydes over ketones was also achieved und...
Source: Journal of Organometallic Chemistry - August 25, 2018 Category: Chemistry Source Type: research

Trichlorostannyl complexes of Ruthenium(II): Synthesis, structure, reactivity and computational studies
Publication date: Available online 23 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Nuria Álvarez-Pazos, Gabriele Albertin, Stefano Antoniutti, Jorge Bravo, Soledad García-Fontán, J.M. Hermida-Ramón, Gianluigi ZanardoAbstractTrichlorostannyl complexes [Ru(SnCl3) (Cp')L] (2a-c) were prepared by treatment of optically active half-sandwich chlorocomplexes [RuCl(Cp')L] (1a-c) with an excess of SnCl2.2H2O in ethanol. Treatment of trichlorostannyl complexes 2a-c with NaBH4 afforded trihydridostannyl derivatives [Ru(SnH3) (Cp')L] (3a-c) in moderated yields. Treatment of 2a-c with MgB...
Source: Journal of Organometallic Chemistry - August 24, 2018 Category: Chemistry Source Type: research

Preparation of enantiomerically pure derivatives of (3-amino-1,2-dicarba-closo-dodecaboran-1-yl)acetic acid
Publication date: Available online 24 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Dmitry A. Gruzdev, Veronika O. Ustinova, Evgeny N. Chulakov, Valentina A. Ol'shevskaya, Pavel A. Slepukhin, Galina L. Levit, Victor P. Krasnov, Valery N. CharushinAbstractThe enantiomerically pure N- and C-protected derivatives of planar-chiral (3-amino-1,2-dicarba-closo-dodecaboran-1-yl)acetic acid (>99% ee) have first been obtained in good yields via a combination of HPLC separation and synthetic procedures. Assignment of absolute configuration of the carborane fragments has been made based on the X-ray diffraction d...
Source: Journal of Organometallic Chemistry - August 24, 2018 Category: Chemistry Source Type: research

Computational study on the mechanisms of [2+3] and [2+2] cycloisomerization reaction catalyzed by gold complex
Publication date: Available online 23 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Fengyue Zhao, Kang Lv, Tao LiuAbstractThe reaction mechanisms on the gold-catalyzed [2 + 3] and [2 + 2] cycloisomerization reaction have been computationally investigated by employing density functional theory (DFT) calculations. The stepwise addition of an olefin to the gold-allyl species followed by the selectivity-determining cyclization is calculated to be the most favorable mechanism, though this mechanism was considered as infeasible in the experiment. Our calculated results also support the Hamm...
Source: Journal of Organometallic Chemistry - August 24, 2018 Category: Chemistry Source Type: research

Cyclooctadiene iridium complexes [Cp*Ir(COD)X]+ (X = Cl, Br, I): Synthesis and application for oxidative coupling of benzoic acid with alkynes
Publication date: 1 November 2018Source: Journal of Organometallic Chemistry, Volume 874Author(s): Vera P. Datsenko, Yulia V. Nelyubina, Alexander F. Smol'yakov, Dmitry A. LoginovAbstractThe cyclooctadiene iridium complexes [Cp*Ir(COD)X]PF6 ([1a−c]PF6; X = Cl, Br, I) were synthesized by reactions of Cp*Ir(COD) with halogens followed by a counterion exchange. The cyclooctadiene in these complexes is a thermally labile ligand. Complex [1b]PF6 reacts with trimethylphosphite to give [Cp*Ir{P(OMe)3}2Br]PF6 ([2]PF6) as a result of the cyclooctadiene replacement. The refluxing of [1b]PF6 in 1,2-dichloroethane affo...
Source: Journal of Organometallic Chemistry - August 22, 2018 Category: Chemistry Source Type: research

Five-membered zircona- and titanacycloallenes; their diverse reactivity depending upon the position of substituents
Publication date: Available online 16 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Noriyuki Suzuki, Rikako Kurita, Akiko Kawamura, Tomoyuki Ono, Yoshiro MasuyamaAbstractFive-membered metallacycloallene compounds that are 2,5-disubstituted 1-zirconacyclopenta-2,3-dienes were prepared from (E)-1,4-trialkylsilylbut-1-en-3-ynes in good yields. The structures of these compounds were determined by X-ray diffraction study. Contrary to our previous study on 2,4-disubstituted 1-zirconacyclopenta-2,3-dienes, which gave alkynyl alcohols by the reaction with ketones after hydrolysis, the 2,5-bis(trialkylsilyl) comp...
Source: Journal of Organometallic Chemistry - August 17, 2018 Category: Chemistry Source Type: research

Polymer supported palladium complex as a reusable catalyst for Suzuki coupling
Publication date: Available online 16 August 2018Source: Journal of Organometallic ChemistryAuthor(s): M.K. Renuka, V. GayathriAbstractNovel, simple and efficient catalytic system based on a polymer supported Pd complex of 2,6-bis(benzimidazolyl)pyridine, Pd(PS-BBP)Cl2, was found to be highly active for Suzuki–Miyaura cross-coupling of aryl halides with phenylboronic acids under mild conditions. The catalyst was characterized by CHN analyses, thermogravimetric analyses, BET surface area measurements, ICP-OES, FT-IR and electronic spectral studies. The effect of solvent, base, temperature and catalyst concentration on...
Source: Journal of Organometallic Chemistry - August 17, 2018 Category: Chemistry Source Type: research

Cyclooctadiene iridium complexes [Cp*Ir(COD)X]+ (X = Cl, Br, I): Synthesis and application for oxidative coupling of benzoic acid with alkynes
Publication date: Available online 16 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Vera P. Datsenko, Yulia V. Nelyubina, Alexander F. Smol'yakov, Dmitry A. LoginovAbstractThe cyclooctadiene iridium complexes [Cp*Ir(COD)X]PF6 ([1a−c]PF6; X = Cl, Br, I) were synthesized by reactions of Cp*Ir(COD) with halogens followed by a counterion exchange. The cyclooctadiene in these complexes is a thermally labile ligand. Complex [1b]PF6 reacts with trimethylphosphite to give [Cp*Ir{P(OMe)3}2Br]PF6 ([2]PF6) as a result of the cyclooctadiene replacement. The refluxing of [1b]PF6 in 1,2-dichloroethane ...
Source: Journal of Organometallic Chemistry - August 16, 2018 Category: Chemistry Source Type: research

Synthesis and biological activities of carbonyl cobalt CORMs with selectively inhibiting cyclooxygenase-2
Publication date: Available online 15 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Jili Li, Jinlong Zhang, Qiuping Zhang, Zhongjie Bai, Quanyi Zhao, Zhen Wang, Yonglin Chen, Bin LiuAbstractIn this paper, three kinds of hybrid carbonyl cobalt CO-releasing molecules (CORMs), RCOOCH2C2H[Co2(CO)6] (R = NSAIDs-COOH, 1–11; R = celecoxib derivative-COOH, 15), RSO2(R’) CH2C2H[Co2(CO)6] (R = celecoxib, 12; R = nimesulide, 13) and ROCH2C2H[Co2(CO)6] (R = ferulic acid etheyl ester, 14), were synthesized and characterized by IR, NMR and HRMS. The crystal structures of complexes 9, 11...
Source: Journal of Organometallic Chemistry - August 15, 2018 Category: Chemistry Source Type: research

Syndio-specific polymerization of styrene promoted by rare-earth metal bis(aminobenzyl) complexes bearing pyrrolyl-modified arylamide ligands
Publication date: Available online 15 August 2018Source: Journal of Organometallic ChemistryAuthor(s): Chaopan Wang, Min Li, Zehuai Mou, Yunjie LuoAbstractAcid-base reaction of the rare-earth metal tris(o-dimethylaminobenzyl) complexes Ln (CH2C6H4NMe2-o)3 with 1 equiv. of the pyrrolyl-modified arylamide ligands 2,5-Me2C4H2NSiMe2NHC6H4R (R = H, Cl-p, OMe-p) in toluene gave (2,5-Me2C4H2NSiMe2NC6H5)Ln (CH2C6H4NMe2-o)2 (Ln = Sc (1), Y (2), Lu (3)), (2,5-Me2C4H2NSiMe2NC6H4Cl-p)Y(CH2C6H4NMe2-o)2 (4), and (2,5-Me2C4H2NSiMe2NC6H4OMe-p)Y(CH2C6H4NMe2-o)2 (5) in good isolated yields. These complexes were well-characterized by...
Source: Journal of Organometallic Chemistry - August 15, 2018 Category: Chemistry Source Type: research