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1.
Inorg Chem ; 2020 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-32049496

RESUMO

B-F σ-bond activation of a fluoroborate has been experimentally achieved through reactions with electron-rich iridium(I) and palladium(0) complexes. The selectivity of B-F σ-bond cleavage by iridium complexes was improved through the high nucleophilicity of the iridium center, implying that a different pathway from that of well-accepted F- abstraction was in effect. The palladium(0) complex was found to promote exclusive B-F σ-bond cleavage even at ambient temperature. Density functional theory (DFT) calculations suggested that B-F σ-bond activation occurred through an SN2-type pathway, which is, to our knowledge, the first proposal of SN2-type borate-fluorine σ-bond cleavage mediated by a transition metal complex. The high feasibility of the SN2-type pathway appears to be attributed to the relatively low deformation energy of the transition state. It was also found that countercation Cs+ effectively stabilized the transition state and product by serving as a F- acceptor.

2.
Angew Chem Int Ed Engl ; 59(1): 172-176, 2020 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-31595640

RESUMO

Single-ligand-based electronically conductive porous coordination polymers/metal-organic frameworks (EC-PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π-conjugated EC-MOF containing copper units with mixed trigonal ligands was developed: Cu3 (HHTP)(THQ) (HHTP=2,3,6,7,10,11-hexahydrotriphenylene, THQ=tetrahydroxy-1,4-quinone). The modulated conductivity (σ≈2.53×10-5  S cm-1 with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m2 g-1 ) of the Cu3 (HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor.

3.
Chemistry ; 26(3): 735-744, 2020 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-31599004

RESUMO

The first examples of porous molecular crystals that are assembled through Au⋅⋅⋅Au interactions of gold complex 1 are here reported along with their exchange properties with respect to their guest components. Single-crystal X-ray diffraction (XRD) analyses indicate that the crystal structure of 1/CH2 Cl2 ⋅pentane is based on cyclic hexamers of 1, which are formed through six Au⋅⋅⋅Au interactions. The packing of these cyclic hexamers affords a porous architecture, in which the one-dimensional channel segment contains CH2 Cl2 and pentane as guests. These guests can be exchanged through operationally simple methods under retention of the host framework of 1, which furnished 1/guest complexes with 26 different guests. A single-crystal XRD analysis of 1/eicosane, which contains the long linear alkane eicosane (n-C20 H42 ), successfully provided its accurately modeled structure within the porous material. These host-guest complexes show chromic luminescence with both blue- and redshifted emissions. Moreover, this porous organometallic material can exhibit luminescent mechanochromism through release of guests.

4.
Phys Chem Chem Phys ; 21(41): 22976-22989, 2019 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-31599298

RESUMO

Trinuclear Cr(ii) complex [Cr3(dpa)4Cl2] 1 (Hdpa = dipyridylamine) has two Cr-Cr double bonds linked with each other. DMRG-CASPT2 calculations reproduced its symmetrical structure. The Cr-Cr effective bond order (EBO) was evaluated to be only 0.59 based on the density matrix based on localized orbitals from DMRG-CASSCF orbitals. The CASCI calculations showed a significantly large α-spin population on the terminal Cr atoms as expected but a significantly large ß-spin population on the central Cr atom against expectations. The very small EBO and the presence of a large ß-spin population are not consistent with the simple understanding that 1 has two Cr-Cr double bonds and a quintet ground state, which requests correct understanding of 1 from the viewpoint of chemical bond theory. Comparison of 1 with the allene molecule and allyl radical disclosed that the linked Cr-Cr bonds of 1 resembled the C-C bond of the allyl radical but completely differed from the linked C-C double bonds of allene despite the similar molecular structure. Its N3 analogue [Cr3(dpa)4(N3)2] 2 has non-symmetrical structure with shorter Cr1-Cr2 and longer Cr2-Cr3 bonds unlike 1, indicating that 2 is a valence tautomer of 1. DMRG-CASPT2 could reproduce its non-symmetrical structure but DFT/B3PW91 could not. In 2, the EBO is 0.95 for the shorter Cr1-Cr2 bond and 0.47 for the longer Cr2-Cr3 one. The terminal Cr3 has a very large α spin population, and the other terminal Cr1 has a somewhat large α spin population, but the central Cr2 has a considerably large ß spin population. These results indicate that the Cr1-Cr2 bond conjugates with the Cr2-Cr3 bond, which is inconsistent with the simple understanding that 2 has a quadruple bond between Cr1 and Cr2 and no bond between Cr2 and Cr3. The symmetrical structure has a stronger Cr-X coordinate bond (X = Cl or N3) but less stable Cr3 core than does the non-symmetrical one. The relative stabilities of the symmetrical and the non-symmetrical structures are determined by the balance between stabilization energies from the Cr3 core and the Cr-X coordinate bond. All these findings show that electronic structures and Cr-Cr bonds of 1 and 2 are interesting from the viewpoint of molecular science.

5.
Nat Commun ; 10(1): 4362, 2019 09 25.
Artigo em Inglês | MEDLINE | ID: mdl-31554816

RESUMO

Direct structural information of confined CO2 in a micropore is important for elucidating its specific binding or activation mechanism. However, weak gas-binding ability and/or poor sample crystallinity after guest exchange hindered the development of efficient materials for CO2 incorporation, activation and conversion. Here, we present a dynamic porous coordination polymer (PCP) material with local flexibility, in which the propeller-like ligands rotate to permit CO2 trapping. This process can be characterized by X-ray structural analysis. Owing to its high affinity towards CO2 and the confinement effect, the PCP exhibits high catalytic activity, rapid transformation dynamics, even high size selectivity to different substrates. Together with an excellent stability with turnover numbers (TON) of up to 39,000 per Zn1.5 cluster of catalyst after 10 cycles for CO2 cycloaddition to form value-added cyclic carbonates, these results demonstrate that such distinctive structure is responsible for visual CO2 capture and size-selective conversion.

6.
ACS Omega ; 4(2): 2596-2609, 2019 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-31459495

RESUMO

Density functional theory calculations here elucidated that Cu38-catalyzed NO reduction by CO occurred not through NO dissociative adsorption but through NO dimerization. NO is adsorbed to two Cu atoms in a bridging manner. NO adsorption energy is much larger than that of CO. N-O bond cleavage of the adsorbed NO molecule needs a very large activation energy (ΔG°‡). On the other hand, dimerization of two NO molecules occurs on the Cu38 surface with small ΔG°‡ and very negative Gibbs reaction energy (ΔG°) to form ONNO species adsorbed to Cu38. Then, a CO molecule is adsorbed at the neighboring position to the ONNO species and reacts with the ONNO to induce N-O bond cleavage with small ΔG°‡ and very negative ΔG°, leading to the formation of N2O adsorbed on Cu38 and CO2 molecule in the gas phase. N2O dissociates from Cu38, and then it is readsorbed to Cu38 in the most stable adsorption structure. N-O bond cleavage of N2O easily occurs with small ΔG°‡ and significantly negative ΔG° to form the N2 molecule and the O atom adsorbed on Cu38. The O atom reacts with the CO molecule to afford CO2 and regenerate Cu38, which is rate-determining. N2O species was experimentally observed in Cu/γ-Al2O3-catalyzed NO reduction by CO, which is consistent with this reaction mechanism. This mechanism differs from that proposed for the Rh catalyst, which occurs via N-O bond cleavage of the NO molecule. Electronic processes in the NO dimerization and the CO oxidation with the O atom adsorbed to Cu38 are discussed in terms of the charge-transfer interaction with Cu38 and Frontier orbital energy of Cu38.

7.
Chem Commun (Camb) ; 55(63): 9291-9294, 2019 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-31339130

RESUMO

N-Heterocyclic carbene (NHC) ligands effective for the cross-coupling of nitroarenes were identified. A rational design of the NHC ligand structures enabled significant reduction of catalyst loadings compared with the previous system employing BrettPhos as a phosphine ligand. Experimental and theoretical studies to compare these ligands gave some insights into high activity of the newly developed NHC ligands.

8.
J Comput Chem ; 40(29): 2571-2576, 2019 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-31322762

RESUMO

A dissociative force field for all-atomistic molecular dynamics calculations has been developed to investigate impact fracture of polymers accompanying dissociation of chemical bonds of polymer main chain. Energy of dimer molecules was evaluated as a function of both bond-length b and bond-angle θ by CASPT2 calculations, whose quality is enough to describe dissociation of chemical bonds. Because we found that the bond dissociation energy D decreases with increasing bond-angle, we employed the Morse-type function VBond (b, θ) = {D - VAngle (θ)}[1 - exp{-α(b - b0 ) - ß(b - b0 )2 }] where a quartic function VAngle (θ) = k1 (θ - θ0 ) + k2 (θ - θ0 )2 + k3 (θ - θ0 )3 + k4 (θ - θ0 )4 . This function reproduced well the CASPT2 potential energy surface in a wide range of b and θ. The parameters have been obtained for four popular glassy polymers, polyethylene, poly(methyl methacrylate), poly(styrene), and polycarbonate. © 2019 Wiley Periodicals, Inc.

9.
J Phys Chem A ; 123(32): 7021-7033, 2019 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-31313931

RESUMO

Reaction of NO molecule on M13 and M55 clusters (M = Ru, Rh, Pd, and Ag) was theoretically investigated to elucidate why its reaction behavior depends on the position of metal element in the periodic table. DFT computations show that NO dissociative adsorption occurs on M = Ru and Rh, NO molecular adsorption occurs on M = Pd, and NO dimerization occurs on M = Ag, which agree with experimental findings. The d-band center and d-band top become lower in energy following the order Ru > Rh > Pd > Ag; this is one of the characteristic features of the periodic table. In the Ag cluster, the valence band-top consists of Ag 5s orbital and its energy is higher than the d-band top of Pd. For NO dissociative adsorption, the M-N and M-O bond strengths are crucially important at the transition state and the product, to which the metal d orbital contributes very much. Ru and Rh clusters have a high energy d-band center and d-valence band top, leading to the formation of strong M-N and M-O bonds. Pd and Ag clusters have a low energy d-band center and d-band top, leading to the formation of weak M-N and M-O bonds. Because the Ag cluster has a high energy 5s valence band that can overlap well with the π* + π* MO of ONNO (NO dimer) moiety due to the same symmetry, charge transfer (CT) occurs from the Ag cluster to the π* + π* MO, which is indispensable for NO dimerization. The 4d-valence band top of Ru and Rh clusters does not fit to the π* + π* MO because of the different symmetry. Though the d-valence band top of the Pd cluster can overlap with the π* + π* MO, its energy is low, which is not good for the CT. Thus, the reactivity of metal cluster for NO is determined by the energy and type (4d or 5s) of the valence band top, which both depend on the position of element in the periodic table; accordingly, Ru and Rh clusters are reactive for NO dissociative adsorption, the Ag cluster is reactive for NO dimerization, but the Pd cluster is not reactive for both and only NO molecular adsorption is possible.

10.
J Comput Chem ; 40(24): 2119-2130, 2019 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-31184780

RESUMO

Catalytic synthesis of dihydropyridine by transition-metal complex is one of the important research targets, recently. Density functional theory calculations here demonstrate that nickel(I) hydride complex (bpy)NiI H (bpy = 2,2'-bipyridine) 1 is a good catalyst for hydrosilylation of both quinoline and pyridine. Two pathways are possible; in path 1, substrate reacts with 1 to form stable intermediate Int1. After that, N3 ─C1 bond of substrate inserts into Ni─H bond of 1 via TS1 to afford N-coordinated 1,2-dihydroquinoline Int2 with the Gibbs activation energy (ΔG°‡ ) of 21.8 kcal mol-1 . Then, Int2 reacts with hydrosilane to form hydrosilane σ-complex Int3; this is named path 1A. In the other route (path 1B), Int1 reacts with phenylsilane in a concerted manner via hydride-shuttle transition state TS2 to afford Int3. In TS2, Si atom takes hypervalent trigonal bipyramidal structure. Formation of hypervalent structure is crucial for stabilization of TS2 (ΔG°‡ = 17.3 kcal mol-1 ). The final step of path 1 is metathesis between Ni─N3 bond of Int3 and Si─H bond of PhSiH3 to afford N-silylated 1,2-dihydroproduct and regenerate 1 (ΔG°‡ = 4.5 kcal mol-1 ). In path 2, 1 reacts with hydrosilane to form Int5, which then forms adduct Int6 with substrate through Si-N interaction between substrate and PhSiH3 . Then, N-silylated 1,2-dihydroproduct is produced via hydride-shuttle transition state TS5 (ΔG°‡ = 18.8 kcal mol-1 ). The absence of N-coordination of substrate to NiI in TS5 is the reason why path 2 is less favorable than path 1B. Quinoline hydrosilylation occurs more easily than pyridine because quinoline has the lowest unoccupied molecular orbital at lower energy than that of pyridine. © 2019 Wiley Periodicals, Inc.

11.
Phys Chem Chem Phys ; 21(35): 18816-18822, 2019 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-31187809

RESUMO

Ni-Cu alloy supported on γ-Al2O3 catalysts prepared by high-temperature hydrogen reduction exhibit high catalytic activity and durability for a three-way catalytic reaction under both oxidative and reductive conditions because of their self-regenerating feature. DFT calculations showed that Ni-oxide was reduced to Ni metal by CO in the presence of Cu metal because of the Ni-Cu alloy effect but was not in the absence of Cu metal.

12.
J Am Chem Soc ; 141(25): 9854-9866, 2019 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-31124356

RESUMO

Iridium-catalyzed C-H borylation of THF was theoretically investigated as example of sp3 C-H functionalization. DFT computations show that ß-regioselective borylation occurs more easily than does α-regioselective, as reported experimentally, through oxidative addition of C-H bond to iridium(III) species and reductive elimination of B-C bond. The reductive elimination is both a rate-determining step and a regioselectivity-determining step. The lower energy transition state (TS) of the reductive elimination of ß-boryloxolane arises from the Ir···(ß-oxolanyl) interaction at TS being stronger than the Ir···(α-oxolanyl) one. The Ir···(ß-oxolanyl) interaction being stronger than the Ir···(α-oxolanyl) one is a result of the valence orbital energy of the α-oxolanyl group being higher than that of the ß-oxolanyl group due to antibonding overlap of the valence orbital with O 2p orbital, where SOMO of oxolanyl radical is taken as valence orbital hereinafter. Reactivity of substrate decreases following the order primary (ß) C-H of ethyl ether > primary C-H of n-pentane ∼ secondary (ß) C-H of THF > secondary C-H of cyclopentane > secondary (α) C-H of THF ∼ secondary C-H of n-pentane > secondary (α) C-H of ethyl ether. The primary C-H bond is more reactive than the secondary one because of its smaller steric repulsion and lower energy valence orbital of the primary alkyl group. The ß-C-H bond of THF is more reactive than the secondary C-H bond of cyclopentane because of valence orbital energy of the ß-oxolanyl group being lower than that of the cyclopentyl group. Both steric and electronic factors are important for determining reactivity of substrate. Bidentate ligand consisting of pyridine and N-heterocyclic carbene is predicted to be better than 3,4,7,8-tetramethyl-1,10-phenanthroline used experimentally.

13.
Inorg Chem ; 58(8): 4894-4906, 2019 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-30946577

RESUMO

The unique Rh-Al bond in recently synthesized Rh(PAlP) 1 {PAlP = pincer-type diphosphino-aluminyl ligand Al[NCH2(P iPr2)]2(C6H4)2NMe} was investigated using the DFT method. Complex 1 has four doubly occupied nonbonding d orbitals on the Rh atom and one Rh d orbital largely participating in the Rh-Al bond which exhibits considerably large bonding overlap between Rh and Al atoms like in a covalent bond. Interestingly, Rhδ--Alδ+ polarization is observed in the bonding MO of 1, which is reverse to Rhδ+-Eδ- (E = coordinating atom) polarization found in a usual coordinate bond. This unusual polarization arises from the presence of the Al valence orbital at significantly higher energy than the Rh valence orbital energy. Characteristic features of 1 are further unveiled by comparing 1 with similar Rh complexes RhL(PMe3)2 (2 for L = AlMe2, 3 for L = Al(NMe2)2, 4 for L = BMe2, 5 for L = SiMe3, 6 for L = SiH3, 7 for L = CH3, 8 for L = OMe, and 9 for L = Cl). As expected, 7, 8, and 9 exhibit usual Rhδ+-Eδ- polarization (E = coordinating atom) in the Rh-E bonding MO. On the other hand, the reverse Rhδ--Eδ+ polarization is observed in the Rh-E bonding MOs of 2-5 like in 1, while the Rh-Si bond is polarized little in 6. These results are clearly understood in terms of the valence orbital energy of the ligand. Because the LUMO of 1 mainly consists of the Rh 4dσ, 5s, and 5p orbitals and the Al 3s and 3p orbitals, both Rh and Al atoms play the role of coordinating site for a substrate bearing a lone pair orbital. For instance, NH3 and pyridine coordinate to both Al and Rh atoms with considerably large binding energy. PAlP exhibits significantly strong trans influence, which is as strong as that of SiMe3 but moderately weaker than that of BMe2. The trans influence of these ligands is mainly determined by the valence orbital energy of the ligand and the covalent bond radius of the coordinating E atom.

14.
Chemistry ; 25(15): 3795-3798, 2019 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-30706971

RESUMO

A tungsten silylyne complex having a W≡Si triple bond reacted with two molecules of aldehydes at room temperature to give W-Si-O-C four-membered metallacycles by [2+2] cycloaddition and subsequent formyl hydrogen transfer from one aldehyde molecule to another. Upon heating to 70 °C, the four-membered metallacycles underwent metathesis-like fragmentation cleanly to afford carbyne complexes and "silanoic esters," in a manner similar to that of metallacyclobutadiene, an intermediate of alkyne metathesis reactions, and dimerization of the latter products gave 1,3-cyclodisiloxanes. The "silanoic ester" was also trapped by pivalaldehyde to give a [2+2] cycloaddition product in high yield.

15.
Science ; 363(6425): 387-391, 2019 01 25.
Artigo em Inglês | MEDLINE | ID: mdl-30679369

RESUMO

Design of the gas-diffusion process in a porous material is challenging because a contracted pore aperture is a prerequisite, whereas the channel traffic of guest molecules is regulated by the flexible and dynamic motions of nanochannels. Here, we present the rational design of a diffusion-regulatory system in a porous coordination polymer (PCP) in which flip-flop molecular motions within the framework structure provide kinetic gate functions that enable efficient gas separation and storage. The PCP shows substantial temperature-responsive adsorption in which the adsorbate molecules are differentiated by each gate-admission temperature, facilitating kinetics-based gas separations of oxygen/argon and ethylene/ethane with high selectivities of ~350 and ~75, respectively. Additionally, we demonstrate the long-lasting physical encapsulation of ethylene at ambient conditions, owing to strongly impeded diffusion in distinctive nanochannels.

16.
J Comput Chem ; 40(1): 181-190, 2019 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-30378149

RESUMO

Experimentally observed NO dimerization on Cu and Ag surfaces is surprising because binding energy of NO dimer is very small in gas phase. MRMP2, MP2 to MP4, CCSD(T), and DFT studies of NO dimerization on Ag2 and Cu2 clusters disclosed that the CCSD(T) method could be applied to this reaction on Ag2 and Cu2 unlike NO dimerization in gas phase which exhibits significantly large nondynamical electron correlation effect. Charge-transfer (CT) from Ag2 and Cu2 to NO moieties plays important role in NN bond formation between two NO molecules. This CT considerably decreases nondynamical correlation effect. Also, the DFT method could be applied to this NO dimerization, if appropriate DFT functional is used; all pure functionals examined here and most of the hybrid functionals underestimated the activation barrier (Ea ), while only ωB97X provided Ea similar to CCSD(T)-calculated value. NO dimerization on similar Cu2 and Cu5 needs moderately larger Ea than those on Ag2 and Ag5 , because frontier orbital participating in the CT exists at lower energy in Cu2 and Cu5 than in Ag2 and Ag5 . The Ea decreases in the order Ag2 >> Ag38 > Ag7 ∼ Ag5 and the reaction energy (ΔE) is positive (endothermic) in Ag2 but significantly negative in Ag38 , Ag7 , and Ag5 , indicating that various Ag clusters could be effective for NO dimerization except for Ag2 . The decreasing order of Ea and increasing order of exothermicity are attributed to increasing order of the frontier orbital energy of Ag2 < Ag38 < Ag7 ∼ Ag5 . © 2018 Wiley Periodicals, Inc.

17.
Chem Sci ; 9(38): 7528-7539, 2018 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-30319753

RESUMO

The concept of chemical topology has generated considerable interest among chemists and one of the state-of-the-art topics is Möbius topology in cyclic π-conjugated molecules. In this regard, expanded porphyrins have been extensively studied because of their facile topological interconversions and attractive optoelectronic properties. A typical example involves [28]hexaphyrins: they show topological conversion between planar Hückel and twisted Möbius topologies owing to their flexible structure. With this in mind, we designed a [28]hexaphyrin where one dimethine pyrrole unit was replaced with dithieno[3,4-b:3',4'-d]thiophene (ß-DTT), aiming at a reversible switching between macrocyclic and cross-conjugated π-systems by a change in molecular topologies. Considering that the ß-DTT unit can offer both macrocyclic and cross-conjugated π-circuits, we envisioned that a combination of the topological interconversion of [28]hexaphyrin with the two π-circuits of the ß-DTT unit would enable a reversible switching between macrocyclic and cross-conjugated π-circuits on Möbius and Hückel topologies, respectively, by a simple conformational change. Unexpectedly, the hexaphyrin revealed a unique, unprecedented π-system switching between a Möbius cross-conjugated π-system and a Hückel antiaromatic π-system, which was fully supported by both experimental and theoretical investigations. Meanwhile, the [28]hexaphyrin was also found to be redox interconvertible with the corresponding [26]hexaphyrin with a Hückel cross-conjugated π-system. These results demonstrate that the ß-DTT unit is a new effective motif to realize π-system switching by changing molecular and π-system topologies. Importantly, external stimuli, i.e., solvent, as well as oxidation/reduction can be used to trigger the topological changes in expanded porphyrins with the help of the ß-DTT unit.

18.
J Am Chem Soc ; 140(42): 13958-13969, 2018 10 24.
Artigo em Inglês | MEDLINE | ID: mdl-30264569

RESUMO

The gate-opening adsorption mechanism and sigmoidal adsorption isotherm were theoretically investigated taking CO2 adsorption into porous coordination polymers, [Fe(ppt)2] n (PCP-N, Hppt = 3-(2-pyrazinyl)-5-(4-pyridyl)-1,2,4-triazole) and [Fe(dpt)2] n (PCP-C, Hdpt = 3-(2-pyridinyl)-5-(4-pyridyl)-1,2,4-triazole) as examples, where the hybrid method consisting of dispersion-corrected DFT for infinite PCP and a post-Hartree-Fock (SCS-MP2 and CCSD(T)) method for the cluster model was employed. PCP-N has site I (one-dimensional channel), site II (small aperture to site I), and site III (small pore) useful for CO2 adsorption. CO2 adsorption at site I occurs in a one by one manner with a Langmuir adsorption isotherm. CO2 adsorption at sites II and III occurs through a gate-opening adsorption mechanism, because the crystal deformation energy ( EDEF) at these sites is induced largely by the first CO2 adsorption but induced much less by the subsequent CO2 adsorption. Interestingly, nine CO2 molecules are adsorbed simultaneously at these sites because a large EDEF cannot be overcome by adsorption of one CO2 molecule but can be by simultaneous adsorption of nine CO2 molecules. For such CO2 adsorption, the Langmuir-Freundlich sigmoidal adsorption isotherm was derived from the equilibrium equation for CO2 adsorption. A very complicated CO2 adsorption isotherm, experimentally observed, is reproduced by combination of the Langmuir and Langmuir-Freundlich adsorption isotherms. In PCP-C, CO2 adsorption occurs only at site I with the Langmuir adsorption isotherm. Sites II and III of PCP-C cannot be used for CO2 adsorption because a very large EDEF cannot be overcome by simultaneous adsorption of nine CO2 molecules. Factors necessary for gate-opening adsorption mechanism are discussed on the basis of differences between PCP-N and PCP-C.

20.
J Am Chem Soc ; 140(23): 7070-7073, 2018 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-29792688

RESUMO

We report rhodium complexes bearing PAlP pincer ligands with an X-type aluminyl moiety. IR spectroscopy and single-crystal X-ray diffraction analysis of a carbonyl complex exhibit the considerable σ-donating ability of the aluminyl ligand, whose Lewis acidity is confirmed through coordination of pyridine to the aluminum center. The X-type PAlP-Rh complexes catalyze C2-selective monoalkylation of pyridine with alkenes.

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