Article
Chemistry, Inorganic & Nuclear
Qingqing Wen, Bin Feng, Li Xiang, Xuebing Leng, Yaofeng Chen
Summary: In this paper, the synthesis and structural characterization of a divalent ytterbium hydrido complex supported by a bulky beta-diketiminato-based tetradentate ligand are reported. This hydrido complex shows versatile reactivity, undergoing hydrido shift reactions and reacting with various compounds such as pyridine and pyridine derivatives. The reactions of this hydrido complex with Ph3P=O and Ph3P=S demonstrate different redox reactions, with the hydrido coupling-based redox reaction found to occur prior to the ytterbium(II) oxidation-based redox reaction when reacted with PhSSPh.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Ritu Yadav, Bindusagar Das, Ashi Singh, Ankita Anmol, Ankita Sharma, Chinmoy Majumder
Summary: In this study, the synthesis and characterization of bicyclic (alkyl)(amino)carbene (BICAAC)-stabilized phosphinidenes were reported. The compounds were obtained through reactions between trihalophosphine and BICAAC, and their structures were confirmed by X-ray crystallography and NMR spectroscopy. Theoretical calculations revealed the presence of predominant C(carbene)-P double bond characteristic in these compounds.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ritu Yadav, Bindusagar Das, Ashi Singh, Ankita Anmol, Ankita Sharma, Chinmoy Majumder
Summary: This study reports the synthesis and characterization of BICAAC-stabilized phosphinidenes. X-ray crystallography and NMR spectroscopy were used to characterize the compounds, and theoretical calculations indicated the presence of characteristic double bonds.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Jun Zhu, Rui Zhang, Guangbin Dong
Summary: A rare reversible C-C single-bond metathesis reaction catalyzed by ruthenium was reported, enabling the synthesis of biaryl compounds under redox-neutral and pH-neutral conditions. The reaction mode involves unexpected 18-electron closed-shell intermediates and is expected to inspire the development of more general C-C single-bond metathesis and orthogonal cross-coupling reactions.
Article
Chemistry, Multidisciplinary
Anthony P. Deziel, Sahil Gahlawat, Nilay Hazari, Kathrin H. Hopmann, Brandon Q. Mercado
Summary: This study compares the rates of CO2 insertion into various metal alkyl bonds and provides fundamental information for the development of new catalysts for CO2 utilization.
Review
Chemistry, Multidisciplinary
Robin N. Perutz, Sylviane Sabo-Etienne, Andrew S. Weller
Summary: This article introduces the concept of sigma-CAM and a new approach to reaction mechanisms. It focuses on the characteristics and dynamic rearrangements of sigma-bond complexes, providing examples of the sigma-CAM mechanism supported by experimental and computational evidence. The authors also critically compare alternative mechanisms for metathesis of metal-element bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexander N. Selikhov, Polina Pechenkina, Anton Cherkasov, Yulia Nelyubina, Tatyana A. Kovylina, Alexander A. Trifonov
Summary: This article reports the synthesis of a series of new half-sandwich bis(alkyl) rare-earth metal complexes and finds that some of these compounds show excellent catalytic activity in α-olefin polymerization reactions and olefin hydrogenation reactions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Jun Zhu, Yibin Xue, Rui Zhang, Benjamin L. Ratchford, Guangbin Dong
Summary: This article describes a catalytic method for activating unstrained and nonpolar C-C bonds, using removable directing groups to aid in the hydrogenolysis of unstrained C(aryl)-C(alkyl) bonds in 2,2'-methylenediphenols. The method yields high amounts of monophenol products and is tolerant of a wide range of functional groups. Additionally, the reaction is scalable and the catalyst loading can be reduced to as low as 0.5 mol %. The method also proves effective in cleaving C(aryl)-C(alkyl) linkages in both phenolic resins and commercial novolacs resins. Experimental and computational mechanistic studies show that the transformation occurs through a directed C(aryl)-C(alkyl) oxidative addition pathway, with C-H activation being a competitive but reversible off-cycle reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Miguel A. Esteruelas, Ana M. Lopez, Enrique Onate, Esther Raga
Summary: This study investigates the silylation mechanism of OsH6((PPr3)-Pr-i)(2) phosphine ligand via net-metathesis reactions, where the silyl group is replaced by a methyl group. The results reveal selective displacement of the silyl substituent, providing insights into the activation and selectivity of the Si-H bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Dong Lu, Songhua Chen, Niu Tang, Shuang-Feng Yin, Nobuaki Kambe, Renhua Qiu
Summary: In this study, a method for producing 2-haloalkoxy-3-substituted quinolines via cyclization of 2-alkynylanilines with TMSCF3 and THF was described. This synthetic method utilizes inexpensive and easy-to-handle TMSCF3 and a commercially available CuI catalyst to efficiently transform a wide range of 2-alkynylanilines into versatile 2-difluoromethoxy-3-substituted quinolines and 2-iodoalkoxy-3-substituted quinolines with excellent chemoselectivity.
Article
Chemistry, Organic
Yu-Zhong Yang, Yang Li, Gui-Fen Lv, De-Liang He, Jin-Heng Li
Summary: A nickel-catalyzed C-S reductive cross-coupling reaction has been developed for the synthesis of alkyl aryl thioethers from alkyl halides and arylthiosilanes. This reaction involves umpolung transformations of arylthiosilanes followed by C-S reductive cross-coupling with alkyl halides to form C(sp(3))-S bond. It exhibits exquisite chemoselectivity, excellent tolerance of diverse functional groups, and wide applications for the late-stage modification of biologically relevant molecules.
Article
Chemistry, Multidisciplinary
Giuseppe Dilauro, Francesco Messa, Fabio Bona, Serena Perrone, Antonio Salomone
Summary: A simple cobalt complex, Co(phen)Cl₂, has been found to be a highly efficient and cost-effective precatalyst for various cross-coupling reactions involving aromatic and aliphatic organoaluminum reagents with aryl, heteroaryl, and alkyl bromides. New C(sp²)-C(sp²) and C(sp²)-C(sp³) bonds can be formed in good to excellent yields and high chemoselectivity under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Takumi Nakajima, Ken Takano, Hiromu Maeda, Yohei Ogiwara, Norio Sakai
Summary: The study shows that disilathiane is effective in mediating the synthesis of alkyl aryl sulfides, promoting cleavage of disulfides to generate thiosilane. Diselenides can also be used in this transformation to produce corresponding selenides.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jonathan D. Bell, Iain Robb, John A. Murphy
Summary: Highly selective photocatalytic functionalisations of alkyl groups in aryl alkyl ethers have been achieved using a phosphate-based acridinium catalyst and visible light irradiation. The reaction proceeds through direct single-electron oxidation and subsequent deprotonation steps, resulting in a wide range of functionalised products in good to excellent yield.
Article
Chemistry, Physical
Wiebke Wackerow, Zeynabou Thiam, Edy Abou-Hamad, Walid Al Maksoud, Mohamed N. Hedhili, Jean-Marie Basset
Summary: The article discusses the unique catalytic properties of tungsten-hydrides supported on oxide supports, suggesting that supported tungsten-hydride complexes coexist on the support as bis-hydride and tris-hydride species.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Multidisciplinary
Tatyana V. Balashova, Svetlana K. Polyakova, Vasily A. Ilichev, Andrey A. Kukinov, Roman V. Rumyantcev, Georgy K. Fukin, Artem N. Yablonskiy, Mikhail N. Bochkarev
Summary: A series of heteroligand complexes were synthesized and structurally characterized. Upon UV excitation, these complexes exhibited fluorescence in the visible region, and some of them also showed a long-lived phosphorescent band. The complexes of Nd, Sm, and Yb displayed metal-centered luminescent f-f transitions.
AUSTRALIAN JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ivan Basalov, Alexander A. Kissel, Elena N. Nikolaevskaya, Nikolai O. Druzhkov, Anton Cherkasov, Jerome Long, Joulia Larionova, Georgy K. Fukin, Alexander A. Trifonov
Summary: The reactions of 2-imino-2,3-dihydrobenzoxazole with compounds containing Yb, Ca, and Y result in the formation of various coordination complexes, involving the opening of the dihydrobenzoxazole ring, elimination of nitrogen sources, and activation of C-H bonds.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Tatiana S. Pochekutova, Georgy K. Fukin, Evgeny Baranov, Boris Petrov, Nikolay M. Lazarev, Vyacheslav K. Khamylov
Summary: In this study, two new barium beta-diketonate complexes were synthesized and characterized using various analytical techniques. It was found that the mutual arrangement of the beta-diketonate ligands relative to the barium atoms differed between the two complexes, and the less favorable conformation was stabilized in the crystal through higher energy of intermolecular interactions.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Inorganic & Nuclear
Tatyana Astaf'eva, Roman Rumyantcev, Maxim Arsenyev, Maxim A. Zherebtsov, Georgy K. Fukin, Vladimir K. Cherkasov, Andrey Poddel'sky
Summary: New triphenylantimony(V) catecholates 1-3 based on 3-formyl-substituted catechols L-1-L-3 have been synthesized and characterized. The formation of 1D-polymer structures for 1, 2 is observed due to the intermolecular donor-acceptor bond of Sb center dot center dot center dot O with the formyl oxygen of the neighboring catecholate molecule.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Georgy K. Fukin, Anton V. Cherkasov, Roman V. Rumyantcev
Summary: Replacing experimental electron density with theoretical one on the terbium atom accurately describes the experimental topology in the coordination sphere, especially in cases of high residual electron density on heavy metal atoms.
MENDELEEV COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexander N. Selikhov, Anton Cherkasov, Konstantin A. Lyssenko, Alexander A. Trifonov
Summary: A series of base-free Ln(III) tris(benzhydryl) complexes were synthesized and their reactions with Bronsted and Lewis acids were investigated.
Article
Chemistry, Multidisciplinary
G. A. Gurina, A. Markin, A. Cherkasov, A. M. Ob'edkov, A. A. Trifonov
Summary: In this study, a scandium chloride complex containing a dianionic bis(phenolate)-tethered N-heterocyclic carbene (NHC) ligand was synthesized and its molecular structure was determined by X-ray diffraction. Under moist air, the NHC moiety undergoes hydrolysis, resulting in the formation of a chloride complex with a dianionic tetradentate bis(phenolate) ligand containing a [NH(CH)(2)N(HC=O)] linker.
RUSSIAN CHEMICAL BULLETIN
(2022)
Article
Chemistry, Inorganic & Nuclear
Ivan V. Lapshin, Anton V. Cherkasov, Alexander A. Trifonov
Summary: Treatment of 4,5-dimethyl-1,3-bis(2-pyridylmethyl)-1H-imidazolium chloride with M[N(SiMe3)2]2(THF)2 (M = Ca, Yb) in 1:2 molar ratio results in the formation of a carbene fragment, activation of the picolyl CH bond, and dearomatization of one of the pyridine rings and affords bis(amido) complexes [(NHC)MN(SiMe3)2]2 (M = Ca (2), Yb (3)) coordinated by a mu 2-bridging pincer NHC amido ligand. Complexes 2 and 3 demonstrate high catalytic activity and excellent regio- and chemoselectivities in the intermolecular hydrophosphination of styrene with both primary and secondary phosphines. Complexes 2 and 3 enable selective addition of PhPH2, Ph2PH, (CH2)4NH, and (CH2)5NH to para-divinylbenzene with high conversions under mild conditions. Tandem hydrophosphination/hydroamination of para-divinylbenzene was also performed.
Article
Chemistry, Inorganic & Nuclear
Dmitry M. Lyubov, Dmitry O. Khristolyubov, Anton V. Cherkasov, Alexander A. Trifonov
Summary: A series of Sc(III) and Y(III) heteroalkyl complexes were synthesized and their structures were determined by single crystal X-ray analysis. The reactivity of different Ln-C (diphenylmethanide vs alkyl or benzyl) bonds towards PhSiH3 was investigated. It was found that the sigma-bond metathesis reactions of certain complexes with PhSiH3 selectively involved Ln-C-Alkyl/Benzyl bonds, while the Ln-C-Ar2 bonds remained intact.
Article
Chemistry, Inorganic & Nuclear
O. Yu. Trofimova, A. V. Maleeva, K. V. Arsen'eva, A. V. Klimashevskaya, A. V. Cherkasov, A. V. Piskunov
Summary: New heteroleptic metal-organic frameworks of lanthanides with anionic organic ligands of two types are synthesized by solvothermal synthesis in N,N-dimethylformamide (DMF). The structures of three compounds, including a cross-linked coordination polymer and two scaffold derivatives, are studied by X-ray diffraction (XRD).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Galina A. Gurina, Alexey V. Markin, Anton V. Cherkasov, Ivan A. Godovikov, Anatoly M. Ob'edkov, Alexander A. Trifonov
Summary: Bis(phenolate) ligands containing benzimidazole-2-ylidene and tetrahydropyrimidine-2-ylidene linkers were used to synthesize isolable Sc3+ chloro and alkyl complexes. The chloro complexes (LScCl)-Sc-1,2(solv)(2) were obtained from the reaction of Sc(CH2SiMe3)(3)(THF)(2) with [(LH3)-H-1,2]Cl or by the salt metathesis reactions of ScCl3 with [L-1,L-2]Na-2. The alkyl derivative [(LSc)-Sc-2(CH2SiMe3)](2) was prepared through the alkylation reaction of (LScCl)-Sc-2(THF)(2) with LiCH2SiMe3 or by subsequent reactions of [(LH3)-H-2]Cl with NaN(SiMe3)(2) and Sc(CH2SiMe3)(3)(THF)(2).
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. Katlenok, Maxim L. Kuznetsov, Anton V. Cherkasov, Dmitry M. Kryukov, Nadezhda A. Bokach, Vadim Yu. Kukushkin
Summary: By using X-ray crystallography, the cocrystals 1 center dot C6F6, 2 center dot C6F6, and 1 center dot(OFA)(2) were obtained by crystallizing the half-lantern Pt-2(II) complexes with electron-deficient arenes. The structural data revealed the occurrence of π-π stacking between the arenes and metal square-planes. Density functional theory calculations and orbital interaction analysis confirmed the contribution of noncovalent bonding and charge-transfer interaction in the overall stacking forces.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. Katlenok, Maxim L. Kuznetsov, Anton V. Cherkasov, Dmitry M. Kryukov, Nadezhda A. Bokach, Vadim Yu. Kukushkin
Summary: In this study, it was observed by X-ray crystallography that the Pt-2(II) complexes form crystals with electron-deficient arenes, and it was verified that there is a π-π stacking interaction between the arenes and the metal square-planes. Density functional theory calculations confirmed the contribution of the noncovalent bond between the arenes and Pt(II) in the overall stacking forces. Orbital interaction analysis demonstrated the significance of the charge-transfer interaction between d(z)(2)(Pt) and pi*(C), attributing the C.Pt contact to a metal-involved tetrel bonding. Many-body interaction analysis showed a positive cooperative effect between the fragments of the half-lantern complex and the perfluoroarenes favoring the occurrence of supramolecular chains.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
I. V. Ershova, A. V. Maleeva, R. R. Aysin, A. V. Cherkasov, A. V. Piskunov
Summary: The synthesis and detailed characterization of a five-coordinated gallium(III) complex (AP(Me))GaI(bipy) have been presented in this study. The complex contains two redox-active ligands, 4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-iminobenzoquinone dianion (AP(Me)) and 2,2'-bipyridyl, along with an iodine atom in the coordination sphere. The molecular structure of the compound was determined through single-crystal X-ray diffraction analysis. Compound 1 exhibits stability in the crystalline state, but decomposes in solution due to symmetrization. The difference in color observed between the crystalline and solution states is attributed to possible intermolecular charge transfer in the crystalline state.
RUSSIAN CHEMICAL BULLETIN
(2023)
