期刊,Journal of Organometallic Chemistry 2022年968/969卷期_国家学术搜索

期刊信息/Journal information

Journal of Organometallic Chemistry

Elsevier Sequoia S. A.

主办单位：Elsevier Sequoia S. A.

国际刊号：0022-328X

Journal of Organometallic Chemistry/Journal Journal of Organometallic ChemistrySCICCRAHCIEI

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Activation of carbon-carbon bonds in d(9) (Co, Rh, Ir) and d(8) (Ru) metal coordinated bicyclo[3.2.1]octa-2,6-diene via agostic M-H-C and M-H interactions

Fazlur-Rahman, A. K.Bennett, Martin A.

13页

查看更多>>摘要：This contribution reveals the first synthesis, protonation reactions and skeletal rearrangements of a series of [M(eta(5)-C5R5)(eta(2):eta(2)-bicyclo[3.2.1]octa-2,6-diene or 2,6-bcod)(M=Co, Rh, Ir, R=H, Me)] 1-3 and [Ru(eta(6)-arene)(eta (2):h(2)-bicyclo[3.2.1]octa-2,6-diene)(arene= C6Me6, C6Me4H2, C6H3Me3)]( )4 complexes. Monoprotonation of these coordinated bicyclo[3.2.1]octa-2,6-diene or 2,6-bcod complexes, 1,3,4 with super acids such as HPF6 (60% aq), HBF4 center dot Et2O or CF3SO3H at low temperature (-80 degrees to -20 degrees C) forms agostic M-H-C structures for [Rh(p-H)(eta(5)-C5R5)(eta(2):h(2)-2,6-bcod)[(+) 5, [Co(mu-H)(h(5)-C5H5)(h(2): h(2)-2,6-bcod)](+) 6 and [Ru(mu-H)(eta(6)-arene)(eta(2):h(2)-2,6-bcod)](+), 7. Similar reactions of 2a, b with the 5d transition metals gave terminal hydride complexes [Ir(H)(eta(5)-C5Me5)(eta(2):h(2)-2,6-bcod)][PF6] 8a, b as isolable salts at room temperature. Initial products of all these monoprotonated cationic salts 5 - 8, undergo isomerization via hydride migration and subsequent cleavage of carbon-carbon bonds to the corresponding eta(2)-vinyl eta(3)-cyclohexenyl cations 9 - 12, independent of the non-coordinating anions. All metal coordinated eta(2)-vinyl, eta(3)-cyclohexenyl cations were isolated and characterized by H-1 and C-13 NMR spectroscopic methods. The structure of 9b was solved by X-ray crystallographic analysis. Nucleophilic addition of H- to the [Ruthenium(eta(2)-hexamethyl)(eta(2)-vinyl eta(3)-cyclohexenyl)]PF6 cation, 12c resulted in the formation of 5-ethyl-eta(4)-1,3-cyclohexadiene complex, 14c as the isomerized product. (C) 2022 Elsevier B.V. All rights reserved.

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A perspective on exploration of synthetic reaction pathways of stable metallocarboxylic acids and structural features of MCOOH moiety

Pal, SrijitaDinda, SoumitraGanguly, Sanjib

7页

查看更多>>摘要：Catalytic transformation of CO and steam to CO2 and H 2 takes place in Water-gas shift reaction (WGSR) while the metallozyme-Carbon monoxide dehydrogenase (CODH) catalyses the conversion of atmospheric CO to CO2 with release of 2H + and 2e (-). Both reactions proceed via an intermediate metallocarboxylic acid. Thus, synthetic approaches and related reaction pathways for stabilizing M-COOH bonded complexes are imperative for further development of model systems to carry out CODH activity. This review summarizes the synthesis of structurally characterized hydroxy carbonyls via selective nucleophilic attack of water or alkali at the C-centre of metal carbonyls, insertion of CO2 into M-H bond and insertion of CO into M-OH bond. The proposed pathways as well the nature of M-C, C-O and C-OH bonds in the MCO2H moieties have also been described. Furthermore, stabilization of quite a few hydroxy carbonyls in crystalline state has also found to be attributed to intermolecular hydrogen bonding. (C) 2022 Elsevier B.V. All rights reserved.

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Ferrocene-based modulators of cancer-associated tumor pyruvate kinase M2

Vyas, HetShard, AmitJadhav, JyotikaDas, Rudradip...

14页

查看更多>>摘要：We report the design and synthesis of fifteen novel ferrocene-based triazolopyrimidines and several other studies that establish these molecules as PKM2 modulators. Our ferrocene-based triazolopyrimidines (FTPs) were subjected to interaction with Pyruvate Kinase isoform, PKM2, which is vehemently over expressed in oral, lung, breast, and colorectal cancers. The in silico outcomes and lactate dehydrogenase (LDH) coupled enzyme assay results revealed many of these molecules can be groomed into potential anticancer agents. Additionally, cyclic voltammetry disclosed that these species are redox-active, one of the criteria for metallocenes to act against cancer in general. Single-crystal X-Ray diffraction crystallography studies fully uncovered the 3D crystal lattice structure and their three-dimensional orientation in depth. Successively, in vitro cell viability studies were performed. Some compounds showed higher potency than cisplatin on CAL 27 cells representing human oral squamous cell carcinoma (OSCC). On top of that, these compounds turned out to be cancer-selective as the normal oral epithelial cell line was unaffected even at higher concentrations than the CAL 27 cell line.(c) 2022 Elsevier B.V. All rights reserved.

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Stereochemical control of the diphosphine and alkyne ligands in triruthenium clusters: The effect of reversible CO loss/addition on the ligand distribution in [Ru-3(mu(3),eta(2)-PhCCPh){mu-Ph2PCH(Me)PPh2}(CO)(7,8)]

Rajbangshi, SubasGhosh, ShishirHogarth, GraemeNesterov, Volodymyr V....

12页

查看更多>>摘要：Thermolysis of [Ru-3{mu-Ph2PCH(Me)PPh2}(CO)(10)] (1) in the presence of diphenylacetylene affords the corresponding alkyne-substituted cluster [Ru-3(mu(3),eta(2)-PhCCPh){mu-Ph2PCH(Me)PPh2}(CO)(8)] (2) and its unsaturated counterpart [Ru-3(mu(3), eta(2)-PhCCPh){mu-Ph2PCH(Me)PPh2 }(CO)(7)] ( 3 ), along with the alkyne-coupled complexes [Ru-3{kappa(2)-Ph2PCH(Me)PPh2 }{mu(3),eta(4)-(CPh)(4) }(CO)(4)(mu-CO)(2)] (4) and [Ru-2{mu-Ph2PCH(Me)PPh2}{mu,eta(4)-(CPh)(4)}(CO)(4)] (5). The backbone-modified diphosphine in 2 has facilitated the growth of single crystals of the same and whose molecular structure was established by X-ray crystallography. The Ph2PCH(Me)PPh2 ligand bridges two ruthenium centers and occupies adjacent axial sites at one of the metallic faces. The diphosphine is situated trans to the alkyne ligand that caps the opposite metallic face. X-ray structural analysis of 3 reveals a perpendicular conformation of the alkyne relative to the metal triangle and a bridging diphosphine that coordinates the adjacent equatorial sites of the alkyne-bisected Ru-Ru bond. The kinetics for the conversion of 2 -> 3 + CO under argon have been investigated over the temperature range 298-343 K in toluene. The calculated activation parameters [Delta H-?= 13.3(3) kcal/mol; Delta S-? = - 31(1) eu] are inconsistent with a rate-limiting step involving a dissociative loss of CO. Consistent with earlier reports on the related analog [Ru-3(mu(3), eta(2)-PhCCPh)(mu-Ph2PCH2PPh2)(CO)(7)] by Lavigne and coworkers, the addition of CO to 3 (1 atm CO) at 258 K is rapid and affords 2 with a rate constant of 1.12(2) e(-1)s(-1). Cluster 3 exhibits high reactivity toward 2e donors. Control experiments confirm that 3 reacts with additional PhC = CPh (66 degrees C, 1 h) to give the diruthenium derivative 5 and that 4 also gives 5 in refluxing THF. The reaction of 3 with hydrogen gas (1 atm, 25 degrees C, 20 min) yields the dihydride [H2Ru3(mu(3),eta(2)-PhCCPh){mu-Ph2PCH(Me)PPh2}(CO)(7)] ( 6 ) in 85% yield. Clusters 2-6 were characterized by IR, H-1, and P-31 NMR spectroscopies, and the solid-state structures of 2-5 were established by single-crystal X-ray crystallography. The bonding in clusters 2 and 3 and the thermodynamics for the equilibrium involving 2 reversible arrow 3 + CO have been evaluated by electronic structure calculations. (C) 2022 Elsevier B.V. All rights reserved.

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Synthesis, structures, and photophysical properties of orange-red emissive Cu(I) complexes of 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene (Xantphos) with the substituted N-hetercycle carbene (NHC) ligand

Lu, YinfuWang, JinglanWu, YaqianHe, Haifeng...

9页

查看更多>>摘要：In the present study, a series of the four-coordinate N-hetercycle carbene (NHC) cop-per (I) complexes [Cu(Ph-Im-cyPy)(Xantphos)]PF6 ( P1 ), [Cu(DimBenPh-Im-cyPy)(Xantphos)]PF6 ( P2 ), and [Cu(BenDimBenIm-CNPy)(Xantphos)]PF6 ( P3 ), Ph-Im-cyPy = 3-benzyl-1-(4-cyano-pyridin-2-yl)-1H-imidazolylidene, DimBenPh-Im-cyPy= 3-(3,5-dimethylbenzyl-1-(4-cyano-pyridin-2-yl)-1H-imidazolylidene, BenDimBenIm-CNPy = 3-benzyl-1-(4-cyano-pyridin-2-yl)-1H -5,6-dimethylbenzimidazolylidene, Xantphos = 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene, have been synthesized and characterized. The molecular structures of P1 -P3 have been established by single-crystal X-ray diffraction study. In the solid state, P1 -P3 exhibit orange-red emission in the range of 621-643 nm with shorter excited-state lifetimes (tau) of 5.73-6.42 mu s and the emission quantum yields (Phi) of 1.0-3.9 % at room temperature. Additionally, the photophysical properties are explained by using density functional theory (DFT) and time dependent DFT. (C) 2022 Elsevier B.V. All rights reserved.

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New unsaturated sulfur-containing heterocycles derived from 1,3-dithiane or 1,3,5-trithiane and alpha -ferrocenylvinyl cation generated from ethynylferrocene

Kizas, O. A.Moiseev, S. K.Chaschin, I. S.Godovikov, I. A....

10页

查看更多>>摘要：Ferrocenylacetylene 1 protonates a superacidic polymer Nafion in sc-CO2 (35 ?, 9 MPa) to form the alpha-ferrocenylvinyl cation, FcC(+) = CH2 ( 2 , Fc = ferrocenyl). Carbocation 2 alkenylates in situ 1,3-dithiane or 1,3,5-trithiane (35 ?, 35 MPa) to give the mono and disulfonium salts with Nafion anion. An anion exchange in the last ones for tetrafluoroborate afforded the disulfonium salts 4 and 12 , whose deprotonation produced, after a sequence of transformations, the neutral unsaturated 8-membered heterocycles, 2-ferrocenyl-3,7-dithiacyclooct-1-ene 10 and 2-ferrocenyl-3,5,7-tritiacyclooct-1-ene 14 . Along with 14 , the reaction of 1 with 1,3,5-trithiane furnished two other neutral sulfur heterocycles, 2,4-diferrocenyl5-thiacyclohexa-1,3-diene 18 , and 1-ferrocenyl-3,5-dithiacyclohex-1-ene 23 . These transformations proceed at room temperature via the C-S bond scission followed by a formation of new C -C bond. Compounds 10, 14, 18, 23 were fully characterized by the NMR spectra. The molecular structures of 10, 14, 18, 23 were elucidated by X-ray study. (c) 2022 Published by Elsevier B.V.

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