C-H and Si-H Activation Reactions at Ru/Ga Complexes: A Combined Experimental and Theoretical Case Study on the Ru-Ga Bond

Overview

Journal Chemistry

Specialty Chemistry

Date 2022 Jun 24

PMID 35748293

Authors

Maximilian Muhr

Raphael Buhler

Hao Liang

Jonas Gilch

Christian Jandl

Samia Kahlal

Jean-Yves Saillard

Christian Gemel

Roland A Fischer

Affiliations

Soon will be listed here.

Abstract

Treatment of [Ru(COD)(MeAllyl) ] and [Ru(COD)(COT)] with GaCp* under hydrogenolytic conditions leads to reactive intermediates which activate Si-H or C-H bonds, respectively. The product complexes [Ru(GaCp*) (SiEt )H ] (1) and [Ru(GaCp*) (C H )H ] (2) are formed with HSiEt or with toluene as the solvent, respectively. While 1 was isolated and fully characterized by NMR, MS, IR and SC-XRD, 2 was too labile to be isolated and was observed and characterized in situ by using mass spectrometry, including labelling experiments for the unambiguous assignment of the elemental composition. The structural assignment was confirmed by DFT calculations. The relative energies of the four isomers possible upon toluene activation at the ortho-, meta-, para- and CH -positions have been determined and point to aromatic C-H activation. The Ru-Ga bond was analyzed by EDA and QTAIM and compared to the Ru-P bond in the analogue phosphine compound. Bonding analyses indicate that the Ru-GaCp* bond is weaker than the Ru-PR bond.

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References

Fujii I, Semba K, Li Q, Sakaki S, Nakao Y . Magnesiation of Aryl Fluorides Catalyzed by a Rhodium-Aluminum Complex. J Am Chem Soc. 2020; 142(27):11647-11652. DOI: 10.1021/jacs.0c04905. View

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

Ruan Z, Zhang S, Zhu C, Ruth P, Stalke D, Ackermann L . Ruthenium(II)-Catalyzed meta C-H Mono- and Difluoromethylations by Phosphine/Carboxylate Cooperation. Angew Chem Int Ed Engl. 2017; 56(8):2045-2049. DOI: 10.1002/anie.201611595. View

Heiss P, Hornung J, Gemel C, Fischer R . A combinatorial coordination-modulated approach to all-hydrocarbon-ligated intermetallic clusters. Chem Commun (Camb). 2022; 58(27):4332-4335. DOI: 10.1039/d2cc00396a. View

Seki R, Hara N, Saito T, Nakao Y . Selective C-O Bond Reduction and Borylation of Aryl Ethers Catalyzed by a Rhodium-Aluminum Heterobimetallic Complex. J Am Chem Soc. 2021; 143(17):6388-6394. DOI: 10.1021/jacs.1c03038. View

Cammarota R, Vollmer M, Xie J, Ye J, Linehan J, Burgess S . A Bimetallic Nickel-Gallium Complex Catalyzes CO Hydrogenation via the Intermediacy of an Anionic d Nickel Hydride. J Am Chem Soc. 2017; 139(40):14244-14250. DOI: 10.1021/jacs.7b07911. View

Studt F, Abild-Pedersen F, Bligaard T, Sorensen R, Christensen C, Norskov J . Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene. Science. 2008; 320(5881):1320-2. DOI: 10.1126/science.1156660. View

Cadenbach T, Gemel C, Bollermann T, Fernandez I, Frenking G, Fischer R . Organometallic chemistry of Ga(+): formation of an unusual gallium dimer in the coordination sphere of ruthenium. Chemistry. 2008; 14(34):10789-96. DOI: 10.1002/chem.200801328. View

Cadenbach T, Gemel C, Schmid R, Fischer R . Mechanistic insights into an unprecedented C-C bond activation on a Rh/Ga bimetallic complex: a combined experimental/computational approach. J Am Chem Soc. 2005; 127(48):17068-78. DOI: 10.1021/ja055298d. View

10.

Steinke T, Gemel C, Winter M, Fischer R . The clusters [Ma(ECp*)b] (M=Pd, Pt; E=Al, Ga, In): structures, fluxionality, and ligand exchange reactions. Chemistry. 2005; 11(5):1636-46. DOI: 10.1002/chem.200400959. View

11.

Komuro T, Tobita H . Thermal reaction of a ruthenium bis(silyl) complex having a lutidine-based Si,N,Si ligand: formation of a mu-silyl(mu-silylene) diruthenium complex involving a 3c-2e Ru-Si-C interaction. Chem Commun (Camb). 2010; 46(7):1136-7. DOI: 10.1039/b915395k. View

12.

Takaya J, Iwasawa N . Synthesis, Structure, and Catalysis of Palladium Complexes Bearing a Group 13 Metalloligand: Remarkable Effect of an Aluminum-Metalloligand in Hydrosilylation of CO. J Am Chem Soc. 2017; 139(17):6074-6077. DOI: 10.1021/jacs.7b02553. View

13.

Muhr M, Heiss P, Schutz M, Buhler R, Gemel C, Linden M . Enabling LIFDI-MS measurements of highly air sensitive organometallic compounds: a combined MS/glovebox technique. Dalton Trans. 2021; 50(26):9031-9036. DOI: 10.1039/d1dt00978h. View

14.

Grimme S . Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem. 2006; 27(15):1787-99. DOI: 10.1002/jcc.20495. View

15.

Armbruster M, Kovnir K, Friedrich M, Teschner D, Wowsnick G, Hahne M . Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation. Nat Mater. 2012; 11(8):690-3. DOI: 10.1038/nmat3347. View

16.

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

17.

Mayer K, Wessing J, Fassler T, Fischer R . Intermetalloid Clusters: Molecules and Solids in a Dialogue. Angew Chem Int Ed Engl. 2018; 57(44):14372-14393. DOI: 10.1002/anie.201805897. View

18.

Campos J . Bimetallic cooperation across the periodic table. Nat Rev Chem. 2023; 4(12):696-702. DOI: 10.1038/s41570-020-00226-5. View

19.

Prinz J, Pignedoli C, Stockl Q, Armbruster M, Brune H, Groning O . Adsorption of small hydrocarbons on the three-fold PdGa surfaces: the road to selective hydrogenation. J Am Chem Soc. 2014; 136(33):11792-8. DOI: 10.1021/ja505936b. View

20.

FISCHER , Weiss . Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals. Angew Chem Int Ed Engl. 1999; 38(19):2830-2850. DOI: 10.1002/(sici)1521-3773(19991004)38:19<2830::aid-anie2830>3.0.co;2-e. View