Silylation reactions on nanoporous gold <i>via</i> homolytic Si–H activation of silanes

Li, Hongbo; Guo, Han; Li, Zhiwen; Cai, Wu; Li, Jing; Zhao, Chunliang; Guo, Shuangxi; Ding, Yi; He, Wei; Li, Yadong

doi:10.1039/c8sc01427b

Cited by 23 publications

(22 citation statements)

References 61 publications

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“…Interestingly, the involvement of the 1,3 dipole bending vibration in such reactions can actually be predicted by the SVP model, without the expensive direct dynamics calculations. In a recent study, 137 we have shown that reactant bending modes have large overlaps with the reaction coordinate at the transition state, in support of the conclusion of Houk and coworkers. In addition, the SVP model also predicts enhancement effects for several other reactant modes, which are to be confirmed.…”

Section: Implications In Larger Reactionssupporting

confidence: 88%

Control of chemical reactivity by transition-state and beyond

Guo

Liu

2016

Chem. Sci.

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Section: Implications In Larger Reactionssupporting

confidence: 88%

Control of chemical reactivity by transition-state and beyond

Guo

Liu

2016

Chem. Sci.

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“…The activation of hydrosilanes by nanogold catalysts has been utilized in various other applications. Li and co-workers 49 showed that in the presence of catalytic amounts of AuNPore, a dihydrosilane (t-Bu 2 SiH 2 ) adds to the C-O bond of epoxides or oxetanes forming acyclic silyl ethers. It was proposed, based on EPR studies, that the activation of the dihydrosilane within AuNPore occurs via a homolytic path.…”

Section: Miscellaneous Transformations From the Nano Au-catalyzed Actmentioning

confidence: 99%

Nanogold(0)-Catalyzed Addition of Heteroelement σ Linkages to Functional Groups

Stratakis

Lykakis

2019

Synthesis

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In recent years, supported Au nanoparticles and nanoporous Au materials have shown remarkable catalytic activity in the activation of σ heteroelement linkages such as, Si–H, Si–Si, B–B and B–Si, and their subsequent addition to functional groups, primarily π bonds. In this review article we discuss the reaction modes known to date, and attempt to discuss the mechanistic clues of these transformations which are rather unexpected in terms of conventional transition-metal catalysis concepts, given that the catalytic sites are metallic Au(0).1 Introduction2 Activation of Hydrosilanes2.1 Reactions of Hydrosilanes with Alkynes2.1.1 Hydrosilylation2.1.2 Dehydrogenative Coupling2.2 Reactions of Hydrosilanes with Allenes2.3 Reactions of Hydrosilanes with Carbonyl Compounds and Imines2.4 Reactions of Hydrosilanes with α-Diazo Carbonyl Compounds2.5 Miscellaneous Transformations from the Nano Au-Catalyzed Activation of Hydrosilanes3 Activation of Disilanes3.1 Disilylation of Alkynes3.2 Reactions of 1,1,2,2-Tetramethyldisilane with Alkynes4 Activation of Diboranes4.1 Diborylation of Alkenes4.2 Diborylation of Alkynes4.3 Diborylation of Allenes4.4 Diborylation of Methylenecyclopropanes5 Activation of Silylboranes5.1 Silaboration of Alkynes5.2 Silaboration of Allenes5.3 Silaboration of Unactivated Epoxides and Oxetanes5.4 Reactions of Silylboranes with Aromatic Carbonyl Compounds6 Conclusions and Future Perspectives

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“…[6,7] H2 activation and hydrogen transfer reactions are key steps in these catalytic cycles. Several mechanistic studies suggested the formation of gold hydrides as reaction intermediates, both in homogeneous [8] and heterogeneous [9,10,11] processes, but details about their mode of action remain limited.…”

Section: Introductionmentioning

confidence: 99%

Hydride Transfer to Gold: Yes or No? Exploring the Unexpected Versatility of Au⋅⋅⋅H−M Bonding in Heterobimetallic Dihydrides

Rocchigiani

Klooster

Coles

et al. 2020

Chemistry A European J

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The potential for coordination and H-transfer from Cp2MH2 (M = Zr, W) to gold(I) and gold(III) complexes was explored in a combined experimental and computational study. [(L)Au] + cations react with Cp2WH2 giving [(L)Au(κ 2 -H2WCp2)] + (L = IPr (1), cyclic (alkyl)(amino)carbene (2), or phosphines PPh3 (3) and Dalphos-Me (4) [IPr = 1,3-bis(diisopropylphenyl)imidazolylidene; Dalphos-Me = di(1-adamantyl)-2-(dimethylamino)phenyl-phosphine], while [Au(DMAP)2] + (DMAP = p-dimethylaminopyridine) affords the C2-symmetric [Au(κ-H2WCp2)2] + (5). The Dalphos complex 4 can be protonated to give the bicationic adduct 4H, showing Au(I) … H + -N hydrogen bonding. The gold(III) Lewis acid [(C^N-CH)Au(C6F5)(OEt2)] + binds Cp2WH2 to give an Au-H-W σ-complex. By contrast, the pincer species [(C^N^C)Au] + adds Cp2WH2 by a purely dative W→Au bond, without Au···H interaction. The biphenyl-based chelate [(C^C)Au] + forms [(C^C)Au(μ-H)2WCp2] + , with two 2-electron-3-centre W-H … Au interactions and practically no Au-W donor acceptor contribution. In all these complexes strong but polarised W-H bonds are maintained, without H-transfer to gold. On the other hand, the reactions of Cp2ZrH2 with gold complexes led in all cases to rapid H-transfer and formation of gold hydrides. Relativistic DFT calculations were used to rationalize the striking reactivity and bonding differences in these heterobimetallic hydride complexes along with an analysis of their characteristic NMR parameters and UV-Vis absorption properties.

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Silylation reactions on nanoporous gold via homolytic Si–H activation of silanes

Cited by 23 publications

References 61 publications

Control of chemical reactivity by transition-state and beyond

Control of chemical reactivity by transition-state and beyond

Nanogold(0)-Catalyzed Addition of Heteroelement σ Linkages to Functional Groups

Hydride Transfer to Gold: Yes or No? Exploring the Unexpected Versatility of Au⋅⋅⋅H−M Bonding in Heterobimetallic Dihydrides

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