Exploring the size dependence of cyclic and acyclic π-systems on cation–π binding

Vijay, Dolly; Sastry, G. Narahari

doi:10.1039/b713703f

Cited by 148 publications

(93 citation statements)

References 47 publications

(26 reference statements)

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“…In a recent analysis, it was observed that the extent of cation p-interaction seem to dramatically increase as the size of the p-system increases [43]. Similar observations have been made about how the excellent performance of computational [44,45].…”

Section: Calculations On Naphthalene Corannulene and Sumanenesupporting

confidence: 57%

The impact of basis set superposition error on the structure of ππ dimers

Vijay

Sakurai

Sastry

2011

Int J of Quantum Chemistry

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The effect of basis set superposition error (BSSE) on the structure and energy of benzene, naphthalene, corannulene, and sumanene dimer has been analyzed. MP2 method was chosen and the effect is estimated using 6-31G, 6-31G(d), 6-311þG(d), cc-pVDZ, and cc-pVTZ basis sets. The model calculations on benzene dimer indicate that the impact of BSSE on the equilibrium geometry of p-stacked dimers appears to be quite significant. Calculations on larger molecular dimers such as the dimers of naphthalene, corannulene, and sumanene are also studied. The practical implication of the current observation on modeling the macromolecular structure is discussed.

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Section: Calculations On Naphthalene Corannulene and Sumanenesupporting

confidence: 57%

The impact of basis set superposition error on the structure of ππ dimers

Vijay

Sakurai

Sastry

2011

Int J of Quantum Chemistry

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“…6), it was discovered that both the reactivity and degree of asymmetric induction observed in these transformations was strongly correlated with the expanse of the arene within a common catalyst framework, with larger arenes proving more effective. Given the cationic nature of the reaction and fact that larger polycyclic aromatic hydrocarbons bind cations more strongly than their smaller analogs, this trend suggested that stabilizing cation-π interactions were profoundly influencing the degree of asymmetric induction (45).…”

Section: Discussionmentioning

confidence: 99%

Attractive noncovalent interactions in asymmetric catalysis: Links between enzymes and small molecule catalysts

Knowles

Jacobsen

2010

Proc. Natl. Acad. Sci. U.S.A.

676

436

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Catalysis by neutral, organic, small molecules capable of binding and activating substrates solely via noncovalent interactions-particularly H-bonding-has emerged as an important approach in organocatalysis. The mechanisms by which such small molecule catalysts induce high enantioselectivity may be quite different from those used by catalysts that rely on covalent interactions with substrates. Attractive noncovalent interactions are weaker, less distance dependent, less directional, and more affected by entropy than covalent interactions. However, the conformational constraint required for high stereoinduction may be achieved, in principle, if multiple noncovalent attractive interactions are operating in concert. This perspective will outline some recent efforts to elucidate the cooperative mechanisms responsible for stereoinduction in highly enantioselective reactions promoted by noncovalent catalysts.enantioselectivity | H bonding | organocatalysis | transition state stabilization

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“…The relatively low interaction energy of 523 kJ mol À1 calculated for Mg 2+ LC(I) is similar to the one predicted for the p-bonded Mg 2+ benzene complex (455 kJ mol À1 ). 45 As for the singly charged ions, the O4 isomer of Mg 2+ LC is calculated to be more stable than the O2 isomer (G = 803 and 632 kJ mol À1 ). The large energy difference between both isomers suggests that bonding to CQO4 is largely preferred over bonding to CQO2.…”

Section: Mg 2+ Lcmentioning

confidence: 97%

IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)

Günther

Nieto

Berden

et al. 2014

Phys. Chem. Chem. Phys.

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Infrared multiphoton dissociation (IRMPD) spectra of mass selected isolated metal-lumichrome ionic complexes, M q+ LC n with M q+ = Li + , Na + , K + , Rb + , Cs + , Ag + (n = 1), and Mg 2+ (n = 2), are recorded in the fingerprint range. The complexes are generated in an electrospray ionization source coupled to an ion cyclotron mass spectrometer and the IR free electron laser FELIX. Vibrational and isomer assignments of the IRMPD spectra are accomplished by density functional theory calculations at the B3LYP/cc-pVDZ level, which provide insight into the structure, binding energy, bonding mechanism, and spectral properties of the complexes. The two major binding sites identified involve metal bonding to the oxygen atoms of the two available carbonyl groups of LC (denoted O2 and O4). The more stable O4 isomer benefits from an additional interaction with the lone pair of the nearby N5 atom of LC. While M + LC with alkali metals are mainly stabilized by electrostatic forces, the Ag + LC complex reveals additional stabilization arising from partly covalent contributions. Finally, the interaction of Mg 2+ ions with LC is largely enhanced by the doubled positive charge. The frequencies of the CQO stretching modes are a sensitive indicator of both the metal binding site and the metal bond strength.

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Exploring the size dependence of cyclic and acyclic π-systems on cation–π binding

Cited by 148 publications

References 47 publications

The impact of basis set superposition error on the structure of ππ dimers

The impact of basis set superposition error on the structure of ππ dimers

Attractive noncovalent interactions in asymmetric catalysis: Links between enzymes and small molecule catalysts

IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)

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Exploring the size dependence of cyclic and acyclic π-systems on cation–π binding

Cited by 148 publications

References 47 publications

The impact of basis set superposition error on the structure of ππ dimers

The impact of basis set superposition error on the structure of ππ dimers

Attractive noncovalent interactions in asymmetric catalysis: Links between enzymes and small molecule catalysts

IRMPD spectroscopy of metalated flavins: structure and bonding of Mq+–lumichrome complexes (Mq+ = Li+–Cs+, Ag+, Mg2+)

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IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)