Biomedical subjects

Aleksey E Kuznetsov

Publications and source records attributed to Aleksey E Kuznetsov.

6 recordsLinked to original sources

PubMed2004

Multiple aromaticity and antiaromaticity in silicon clusters.

A series of silicon clusters containing four atoms but with different charge states (Si4(2+), Si4, Si4(2-), and NaSi4-) were studied by photoelectron spectroscopy and ab initio calculations. Structure evolution and chemical bonding in this series were interpreted in terms of aromaticity and antiaromaticity, which allowed the prediction of how structures of the four-atom silicon clusters change upon addition or removal of two electrons. It is shown that Si4(2+) is square-planar, analogous to the recently discovered aromatic Al4(2-) cluster. Upon of two electrons, neutral Si4 becomes sigma-antiaromatic and exhibits a rhombus distortion. Adding two more electrons to Si4 leads to two energetically close structures of Si4(2-): either a double antiaromatic parallelogram structure or an aromatic system with a butterfly distortion. Because of the electronic instability of doubly charged Si4(2-), a stabilizing cation (Na+) was used to produce Si4(2-) in the gas phase in the form of Na+[Si4(2-)], which was characterized experimentally by photoelectron spectroscopy. Multiple antiaromaticity in the parallelogram Na+[Si4(2-)] species is highly unusual.

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PubMed2003

All-metal antiaromatic molecule: rectangular Al4(4-) in the Li3Al4(-) anion.

We report the experimental and theoretical characterization of antiaromaticity in an all-metal system, Li3Al4(-), which we produced by laser vaporization and studied with the use of photoelectron spectroscopy and ab initio calculations. The most stable structure of Li3Al4(-) found theoretically contained a rectangular Al4(4-) tetraanion stabilized by the three Li+ ions in a capped octahedral arrangement. Molecular orbital analyses reveal that the rectangular Al4(4-) tetraanion has four pi electrons, consistent with the 4n Hückel rule for antiaromaticity.

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PubMed2002

Peculiar antiaromatic inorganic molecules of tetrapnictogen in Na+Pn4- (Pn = P, As, Sb) and important consequences for hydrocarbons.

Although aromaticity has been observed in inorganic and all-metal species, the concept of antiaromaticity has not been extended beyond organic molecules. Here, we present theoretical and experimental evidence that the 6 -electron tetrapnictogen dianions in Na+Pn42- (Pn = P, As, Sb) undergo a transition from being aromatic to antiaromatic upon electron detachment, yielding the first inorganic antiaromatic Na+Pn4- molecules. Two types of antiaromatic structures were characterized, the conventional rectangular species and a new peculiar quasiplanar rhombus species. Aromaticity and antiaromaticity in the tetrapnictogen molecules were derived from molecular orbital analyses and verified by experimental photodetachment spectra of Na+Pn42-. On the basis of our findings for the tetrapnictogen clusters, we predicted computationally that the organic C4H4- anion also possesses two antiaromatic structures: rectangular and rhombus. Moreover, only the rhombus antiaromatic minimum was found for the radical NC3H4, thus extending the peculiar rhombus antiaromatic structure first uncovered in inorganic clusters into organic chemistry.

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PubMed2002

Al(6)(2-) - fusion of two aromatic Al(3)(-) units. A combined photoelectron spectroscopy and ab initio study of M(+)[Al(6)(2-)] (M = Li, Na, K, Cu, and Au).

Photoelectron spectroscopy is combined with ab initio calculations to elucidate the structure and chemical bonding of a series of MAl(6)(-) (M = Li, Na, K, Cu, and Au) bimetallic clusters. Well-resolved photoelectron spectra were obtained for MAl(6)(-) (M = Li, Na, Cu, and Au) at several photon energies. The ab initio calculations showed that all of the MAl(6)(-) clusters can be viewed as an M(+) cation interacting with an Al(6)(2-) dianion. Al(6)(2-) was found to possess an O(h) ground-state structure, and all of the MAl(6)(-) clusters possess a C(3v) ground-state structure derived from the O(h) Al(6)(2-). Careful comparison between the photoelectron spectral features and the ab initio one-electron detachment energies allows us to establish firmly the C(3v)ground-state structures for the MAl(6)(-) clusters. A detailed molecular orbital (MO) analysis is conducted for Al(6)(2-) and compared with Al(3)(-). It was shown that Al(6)(2-) can be considered as the fusion of two Al(3)(-) units. We further found that the preferred occupation of those MOs derived from the sums of the empty 2e' MOs of Al(3)(-), rather than those derived from the differences between the occupied 2a(1)' and 2a(2)' ' MOs of Al(3)(-), provides the key bonding interactions for the fusion of the two Al(3)(-) into Al(6)(2-). Because there are only four bonding MOs (one pi and three sigma MOs), an analysis of resonance structures was performed for the O(h)Al(6)(2-). It is shown that every face of the Al(6)(2-) octahedron still possesses both pi- and sigma-aromaticity, analogous to Al(3)(-), and that in fact Al(6)(2-) can be viewed to possess three-dimensional pi- and sigma-aromaticity with a large resonance stabilization.

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PubMed2002

Peculiar transformation of a nonaromatic Al(4)Cl(4)(NH(3))(4) into an aromatic Na(2)Al(4)Cl(4)(NH(3))(4).

We analyzed the molecular orbitals for a Al(4)Cl(4)(NH(3))(4) compound, which is a model of the (AlBr x NEt(3))(4) crystal structure recently reported by Schnöckel and co-workers. We found that even though Al(4)Cl(4)(NH(3))(4) contains a planar square Al(4) cluster it is not an aromatic compound. However, the addition of two sodium atoms to Al(4)Cl(4)(NH(3))(4) yields a new Na(2)Al(4)Cl(4)(NH(3))(4) compound which is a pi-aromatic molecule. We hope that prediction of this new compound will facilitate a synthesis of aluminum aromatic solids.

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PubMed2002

On the resonance energy in new all-metal aromatic molecules.

We have recently advanced the aromaticity concept into all-metal molecules containing Al(4)(2-), XAl(3)(-), Ga(4)(2-), In(4)(2-), Hg(4)(6-), Al(3)(-), and Ga(3)(-) aromatic units. All these systems are electron deficient species compared to the corresponding aromatic hydrocarbons. The electron deficiency results in an interesting new feature in all-metal aromatic systems, which should be considered as having both pi- and sigma-aromaticity, and that should result in their additional stability. In this work, we obtain crude evaluations of the resonance energies for Na(2)Al(4) and Na(2)Ga(4) all-metal aromatic molecules. The resonance energies were found to be unusually high: 30 kcal/mol (B3LYP/6-311+G*) and 48 kcal/mol (CCSD(T)/6-311+G(2df)) for Na(2)Al(4) and 21 kcal/mol (B3LYP/6-311+G*) for Na(2)Ga(4) compared to 20 kcal/mol in benzene. We believe that the high resonance energies in Na(2)Al(4) and in Na(2)Ga(4) are due to the presence of three completely delocalized bonds, one pi-bond and two sigma-bonds, thus confirming the presence of pi- and sigma-aromaticity.

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