Bonding Situation of σ-E-H Complexes in Transition Metal and Main Group Compounds

Overview

Journal Chemistry

Specialty Chemistry

Date 2022 Jul 28

PMID 35900796

Authors

Pablo Rios

Salvador Conejero

Israel Fernandez

Affiliations

Soon will be listed here.

Abstract

The ambiguous bonding situation of σ-E-H (E=Si, B) complexes in transition metal compounds has been rationalized by means of Density Functional Theory calculations. To this end, the combination of the Energy Decomposition Analysis (EDA) method and its Natural Orbital for Chemical Valance (NOCV) extension has been applied to representative complexes described in the literature where the possible η versus η coordination mode is not unambiguously defined. Our quantitative analyses, which complement previous data based on the application of the Quantum Theory of Atoms in Molecules (QTAIM) approach, indicate that there exists a continuum between genuine η and η modes depending mainly on the strength of the backdonation. Finally, we also applied this EDA-NOCV approach to related main-group species where the backdonation is minimal.

Citing Articles

Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species.

Padilla M, Batuecas M, Garcia-Orduna P, Fernandez I, Fernandez-Alvarez F Inorg Chem. 2024; 64(1):255-267.

PMID: 39710970 PMC: 11734117. DOI: 10.1021/acs.inorgchem.4c04512.

σ-GeH and Germyl Cationic Pt(II) Complexes.

Laglera-Gandara C, Rios P, Fernandez-de-Cordova F, Barturen M, Fernandez I, Conejero S Inorg Chem. 2022; 61(51):20848-20859.

PMID: 36322561 PMC: 9949701. DOI: 10.1021/acs.inorgchem.2c03186.

Bonding Situation of σ-E-H Complexes in Transition Metal and Main Group Compounds.

Rios P, Conejero S, Fernandez I Chemistry. 2022; 28(57):e202201920.

PMID: 35900796 PMC: 9804526. DOI: 10.1002/chem.202201920.

References

Rios P, Martin-de la Calle R, Vidossich P, Fernandez-de-Cordova F, Lledos A, Conejero S . Reversible carbon-boron bond formation at platinum centers through σ-BH complexes. Chem Sci. 2021; 12(5):1647-1655. PMC: 8179255. DOI: 10.1039/d0sc05522k. View

Kramer F, Radius M, Berberich H, Fernandez I, Breher F . A neutral, acyclic, borataalkene-like ligand for group 11 metals: L- and Z-type ligands side by side. Chem Commun (Camb). 2022; 58(24):3905-3908. DOI: 10.1039/d2cc00199c. View

Yang J, White P, Schauer C, Brookhart M . Structural and spectroscopic characterization of an unprecedented cationic transition-metal eta1-silane complex. Angew Chem Int Ed Engl. 2008; 47(22):4141-3. DOI: 10.1002/anie.200705359. View

Wu X, Zhao L, Jiang D, Fernandez I, Berger R, Zhou M . Barium as Honorary Transition Metal in Action: Experimental and Theoretical Study of Ba(CO) and Ba(CO)<sup/>. Angew Chem Int Ed Engl. 2018; 57(15):3974-3980. DOI: 10.1002/anie.201713002. View

Lipke M, Liberman-Martin A, Don Tilley T . Electrophilic Activation of Silicon-Hydrogen Bonds in Catalytic Hydrosilations. Angew Chem Int Ed Engl. 2016; 56(9):2260-2294. DOI: 10.1002/anie.201605198. View

Fang H, Oestreich M . Defunctionalisation catalysed by boron Lewis acids. Chem Sci. 2021; 11(47):12604-12615. PMC: 8163203. DOI: 10.1039/d0sc03712e. View

Chen J, Chen E . Elusive silane-alane complex [Si-H⋅⋅⋅Al]: isolation, characterization, and multifaceted frustrated Lewis pair type catalysis. Angew Chem Int Ed Engl. 2015; 54(23):6842-6. DOI: 10.1002/anie.201502400. View

Becke . Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A Gen Phys. 1988; 38(6):3098-3100. DOI: 10.1103/physreva.38.3098. View

Rios P, Fouilloux H, Diez J, Vidossich P, Lledos A, Conejero S . σ-Silane Platinum(II) Complexes as Intermediates in C-Si Bond-Coupling Processes. Chemistry. 2019; 25(48):11346-11355. DOI: 10.1002/chem.201902226. View

10.

Liu Y, Su B, Dong W, Li Z, Wang H . Structural Characterization of a Boron(III) η-σ-Silane-Complex. J Am Chem Soc. 2019; 141(20):8358-8363. DOI: 10.1021/jacs.9b03213. View

11.

Plumley J, Evanseck J . Periodic trends and index of boron LEwis acidity. J Phys Chem A. 2009; 113(20):5985-92. DOI: 10.1021/jp811202c. View

12.

Corey J . Reactions of hydrosilanes with transition metal complexes and characterization of the products. Chem Rev. 2011; 111(2):863-1071. DOI: 10.1021/cr900359c. View

13.

Safin D, Babashkina M, Robeyns K, Mitoraj M, Kubisiak P, Garcia Y . Influence of the Homopolar Dihydrogen Bonding C-H⋅⋅⋅H-C on Coordination Geometry: Experimental and Theoretical Studies. Chemistry. 2015; 21(46):16679-87. DOI: 10.1002/chem.201501499. View

14.

Glendening E, Landis C, Weinhold F . NBO 6.0: natural bond orbital analysis program. J Comput Chem. 2013; 34(16):1429-37. DOI: 10.1002/jcc.23266. View

15.

Forster F, Oestreich M . Bioinspired Catalytic Generation of Main-group Electrophiles by Cooperative Bond Activation. Chimia (Aarau). 2018; 72(9):584-588. DOI: 10.2533/chimia.2018.584. View

16.

Oestreich M, Hermeke J, Mohr J . A unified survey of Si-H and H-H bond activation catalysed by electron-deficient boranes. Chem Soc Rev. 2015; 44(8):2202-20. DOI: 10.1039/c4cs00451e. View

17.

Fernandez I, Holzmann N, Frenking G . The Valence Orbitals of the Alkaline-Earth Atoms. Chemistry. 2020; 26(62):14194-14210. PMC: 7702052. DOI: 10.1002/chem.202002986. View

18.

Chen Z, Wannere C, Corminboeuf C, Puchta R, Schleyer P . Nucleus-independent chemical shifts (NICS) as an aromaticity criterion. Chem Rev. 2005; 105(10):3842-88. DOI: 10.1021/cr030088+. View

19.

Perdew . Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys Rev B Condens Matter. 1986; 33(12):8822-8824. DOI: 10.1103/physrevb.33.8822. View

20.

Rios P, Rodriguez A, Conejero S . Activation of Si-H and B-H bonds by Lewis acidic transition metals and p-block elements: same, but different. Chem Sci. 2022; 13(25):7392-7418. PMC: 9241980. DOI: 10.1039/d2sc02324e. View