Lewis Base Activation of Lewis Acid: A Detailed Bond Analysis

Overview

Journal ACS Omega

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Aug 29

PMID 31458265

Citations 2

Authors

Gianluca Ciancaleoni

Affiliations

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Abstract

The effect of a Lewis base (LB) on the nucleophilic attack on chalcogeniranium (chalcogen = sulfur and selenium) cations, the so-called LB activation of a Lewis acid, has been studied coupling natural orbital for chemical valence decomposition of the orbital interaction energy with charge displacement analysis. This methodology provides a detailed and accurate description of all the interactions (LB···chalcogen, chalcogen···olefin and olefin···ammonia) present in the system and leads to a deeper understanding of how they influence each other at all stages of the reaction: reactant complex, transition state, and product complex. In particular, the bond between the chalcogen and the olefin has been decomposed in terms of σ donation/π back-donation and the bond components quantified. This allowed determination of a linear relationship between the activation barrier of the nucleophilic attack and the net amount of charge donated by the olefin to the chalcogen.

Citing Articles

Charge Displacement Analysis-A Tool to Theoretically Characterize the Charge Transfer Contribution of Halogen Bonds.

Ciancaleoni G, Nunzi F, Belpassi L Molecules. 2020; 25(2).

PMID: 31940866 PMC: 7024339. DOI: 10.3390/molecules25020300.

Interplay between Gold(I)-Ligand Bond Components and Hydrogen Bonding: A Combined Experimental/Computational Study.

Marrazzini G, Gabbiani C, Ciancaleoni G ACS Omega. 2019; 4(1):1344-1353.

PMID: 31459403 PMC: 6647975. DOI: 10.1021/acsomega.8b03330.

References

WIRTH . Organoselenium Chemistry in Stereoselective Reactions. Angew Chem Int Ed Engl. 2000; 39(21):3740-3749. DOI: 10.1002/1521-3773(20001103)39:21<3740::aid-anie3740>3.0.co;2-n. View

Bessac F, Frenking G . Why is BCl3 a stronger Lewis acid with respect to strong bases than BF3?. Inorg Chem. 2003; 42(24):7990-4. DOI: 10.1021/ic034141o. View

Denmark S, Edwards M . On the mechanism of the selenolactonization reaction with selenenyl halides. J Org Chem. 2006; 71(19):7293-306. DOI: 10.1021/jo0610457. View

Mitoraj M, Michalak A . Natural orbitals for chemical valence as descriptors of chemical bonding in transition metal complexes. J Mol Model. 2006; 13(2):347-55. DOI: 10.1007/s00894-006-0149-4. View

Murray J, Lane P, Clark T, Politzer P . Sigma-hole bonding: molecules containing group VI atoms. J Mol Model. 2007; 13(10):1033-8. DOI: 10.1007/s00894-007-0225-4. View

Denmark S, Collins W . Lewis base activation of Lewis acids: development of a Lewis base catalyzed selenolactonization. Org Lett. 2007; 9(19):3801-4. DOI: 10.1021/ol701617d. View

Belpassi L, Infante I, Tarantelli F, Visscher L . The chemical bond between Au(I) and the noble gases. Comparative study of NgAuF and NgAu+ (Ng = Ar, Kr, Xe) by density functional and coupled cluster methods. J Am Chem Soc. 2007; 130(3):1048-60. DOI: 10.1021/ja0772647. View

Denmark S, Collins W, Cullen M . Observation of direct sulfenium and selenenium group transfer from thiiranium and seleniranium ions to alkenes. J Am Chem Soc. 2009; 131(10):3490-2. DOI: 10.1021/ja900187y. View

Destro R, Ortoleva E, Soave R, Loconte L, Lo Presti L . Detection and kinetics of the single-crystal to single-crystal complete transformation of a thiiranium ion into thietanium ion. Phys Chem Chem Phys. 2009; 11(33):7181-8. DOI: 10.1039/b901928f. View

10.

Grimme S, Antony J, Ehrlich S, Krieg H . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. 2010; 132(15):154104. DOI: 10.1063/1.3382344. View

11.

Salvi N, Belpassi L, Tarantelli F . On the Dewar-Chatt-Duncanson model for catalytic gold(I) complexes. Chemistry. 2010; 16(24):7231-40. DOI: 10.1002/chem.201000608. View

12.

Allouche A . Gabedit--a graphical user interface for computational chemistry softwares. J Comput Chem. 2010; 32(1):174-82. DOI: 10.1002/jcc.21600. View

13.

Denmark S, Kornfilt D, Vogler T . Catalytic asymmetric thiofunctionalization of unactivated alkenes. J Am Chem Soc. 2011; 133(39):15308-11. PMC: 3187834. DOI: 10.1021/ja2064395. View

14.

Ciancaleoni G, Scafuri N, Bistoni G, Macchioni A, Tarantelli F, Zuccaccia D . When the Tolman electronic parameter fails: a comparative DFT and charge displacement study of [(L)Ni(CO)₃](0/-) and [(L)Au(CO)](0/+). Inorg Chem. 2014; 53(18):9907-16. DOI: 10.1021/ic501574e. View

15.

Denmark S, Hartmann E, Kornfilt D, Wang H . Mechanistic, crystallographic, and computational studies on the catalytic, enantioselective sulfenofunctionalization of alkenes. Nat Chem. 2014; 6(12):1056-64. PMC: 4677329. DOI: 10.1038/nchem.2109. View

16.

Ciancaleoni G, Biasiolo L, Bistoni G, Macchioni A, Tarantelli F, Zuccaccia D . Selectively measuring π back-donation in gold(I) complexes by NMR spectroscopy. Chemistry. 2014; 21(6):2467-73. DOI: 10.1002/chem.201406049. View

17.

Bistoni G, Rampino S, Tarantelli F, Belpassi L . Charge-displacement analysis via natural orbitals for chemical valence: charge transfer effects in coordination chemistry. J Chem Phys. 2015; 142(8):084112. DOI: 10.1063/1.4908537. View

18.

Azzopardi K, Bistoni G, Ciancaleoni G, Tarantelli F, Zuccaccia D, Belpassi L . Quantitative assessment of the carbocation/carbene character of the gold-carbene bond. Dalton Trans. 2015; 44(31):13999-4007. DOI: 10.1039/c5dt02183a. View

19.

Ciancaleoni G, Santi C, Ragni M, Braga A . Charge-displacement analysis as a tool to study chalcogen bonded adducts and predict their association constants in solution. Dalton Trans. 2015; 44(46):20168-75. DOI: 10.1039/c5dt03388h. View

20.

Ciancaleoni G, Rampino S, Zuccaccia D, Tarantelli F, Belanzoni P, Belpassi L . An ab Initio Benchmark and DFT Validation Study on Gold(I)-Catalyzed Hydroamination of Alkynes. J Chem Theory Comput. 2015; 10(3):1021-34. DOI: 10.1021/ct400980w. View