Cyclometalated Gold(iii) Complexes: Noticeable Differences Between (N,C) and (P,C) Ligands in Migratory Insertion

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 May 22

PMID 29780525

Citations 5

Authors

Jordi Serra

Pau Font

E Daiann Sosa Carrizo

Sonia Mallet-Ladeira

Stephane Massou

Teodor Parella

Karinne Miqueu

Abderrahmane Amgoune

Xavi Ribas

Didier Bourissou

Affiliations

Soon will be listed here.

Abstract

Gold(iii) complexes are garnering increasing interest for opto-electronic, therapeutic and catalytic applications. But so far, very little is known about the factors controlling their reactivity and the very influence of the ancillary ligand. This article reports the first comprehensive study on this topic. The reactivity of a cationic (N,C) gold(iii) complex, namely , towards ethylene has been thoroughly studied and compared with that of the related (P,C) complex . A cationic gold(iii) complex resulting from double insertion of ethylene was selectively obtained. Complex was found to be remarkably stable. It was trapped with chloride and fully characterized. In marked contrast to that observed with , no β-H elimination or linear-to-branched rearrangement of the alkyl chain occurred with . The energy profile for the reactions of with ethylene has been comprehensively investigated computationally, and the influence of the ancillary ligand has been precisely delineated. Because nitrogen is a weaker donor than carbon (and phosphorus), the (N,C) ligand is very electronically dissymmetric, much more than the (P,C) ligand. This makes the two reactive sites at gold quite different, which noticeably influences the competition between migratory insertion and β-H elimination, and actually changes the outcome of the olefin insertion at gold. This study provides valuable insight into the influence of ancillary ligands on gold(iii) reactivity, something critical to further develop Au(iii) and Au(i)/Au(iii) catalysis.

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References

Guironnet D, Caporaso L, Neuwald B, Gottker-Schnetmann I, Cavallo L, Mecking S . Mechanistic insights on acrylate insertion polymerization. J Am Chem Soc. 2010; 132(12):4418-26. DOI: 10.1021/ja910760n. View

To W, Chan K, Tong G, Ma C, Kwok W, Guan X . Strongly luminescent gold(III) complexes with long-lived excited states: high emission quantum yields, energy up-conversion, and nonlinear optical properties. Angew Chem Int Ed Engl. 2013; 52(26):6648-52. DOI: 10.1002/anie.201301149. View

Hofer M, Genoux A, Kumar R, Nevado C . Gold-Catalyzed Direct Oxidative Arylation with Boron Coupling Partners. Angew Chem Int Ed Engl. 2016; 56(4):1021-1025. DOI: 10.1002/anie.201610457. View

Sun C, To W, Wang X, Chan K, Su Z, Che C . Metal-organic framework composites with luminescent gold(iii) complexes. Strongly emissive and long-lived excited states in open air and photo-catalysis. Chem Sci. 2018; 6(12):7105-7111. PMC: 5947532. DOI: 10.1039/c5sc02216a. View

Au V, Wu D, Yam V . Organic memory devices based on a bis-cyclometalated alkynylgold(III) complex. J Am Chem Soc. 2015; 137(14):4654-7. DOI: 10.1021/jacs.5b02113. View

Fung S, Zou T, Cao B, Lee P, Fung Y, Hu D . Cyclometalated Gold(III) Complexes Containing N-Heterocyclic Carbene Ligands Engage Multiple Anti-Cancer Molecular Targets. Angew Chem Int Ed Engl. 2017; 56(14):3892-3896. DOI: 10.1002/anie.201612583. View

Wolf W, Winston M, Toste F . Exceptionally fast carbon-carbon bond reductive elimination from gold(III). Nat Chem. 2014; 6(2):159-64. PMC: 3970324. DOI: 10.1038/nchem.1822. View

Szentkuti A, Bachmann M, Garg J, Blacque O, Venkatesan K . Monocyclometalated gold(III) monoaryl complexes--a new class of triplet phosphors with highly tunable and efficient emission properties. Chemistry. 2014; 20(9):2585-96. DOI: 10.1002/chem.201303673. View

Joost M, Amgoune A, Bourissou D . Reactivity of Gold Complexes towards Elementary Organometallic Reactions. Angew Chem Int Ed Engl. 2016; 54(50):15022-45. DOI: 10.1002/anie.201506271. View

10.

Rocchigiani L, Fernandez-Cestau J, Budzelaar P, Bochmann M . Arene C-H activation by gold(iii): solvent-enabled proton shuttling, and observation of a pre-metallation Au-arene intermediate. Chem Commun (Camb). 2017; 53(31):4358-4361. DOI: 10.1039/c7cc01628j. View

11.

Hong E, Poon C, Yam V . A Phosphole Oxide-Containing Organogold(III) Complex for Solution-Processable Resistive Memory Devices with Ternary Memory Performances. J Am Chem Soc. 2016; 138(20):6368-71. DOI: 10.1021/jacs.6b02629. View

12.

Tang M, Lee C, Lai S, Ng M, Chan M, Yam V . Versatile Design Strategy for Highly Luminescent Vacuum-Evaporable and Solution-Processable Tridentate Gold(III) Complexes with Monoaryl Auxiliary Ligands and Their Applications for Phosphorescent Organic Light Emitting Devices. J Am Chem Soc. 2017; 139(27):9341-9349. DOI: 10.1021/jacs.7b04788. View

13.

Boorman T, Larrosa I . Gold-mediated C-H bond functionalisation. Chem Soc Rev. 2010; 40(4):1910-25. DOI: 10.1039/c0cs00098a. View

14.

Bronner C, Wenger O . Luminescent cyclometalated gold(III) complexes. Dalton Trans. 2011; 40(46):12409-20. DOI: 10.1039/c1dt10636h. View

15.

Hopkinson M, Tlahuext-Aca A, Glorius F . Merging Visible Light Photoredox and Gold Catalysis. Acc Chem Res. 2016; 49(10):2261-2272. DOI: 10.1021/acs.accounts.6b00351. View

16.

Rekhroukh F, Brousses R, Amgoune A, Bourissou D . Cationic gold(III) alkyl complexes: generation, trapping, and insertion of norbornene. Angew Chem Int Ed Engl. 2014; 54(4):1266-9. DOI: 10.1002/anie.201409604. View

17.

Noda S, Nakamura A, Kochi T, Chung L, Morokuma K, Nozaki K . Mechanistic studies on the formation of linear polyethylene chain catalyzed by palladium phosphine-sulfonate complexes: experiment and theoretical studies. J Am Chem Soc. 2009; 131(39):14088-100. DOI: 10.1021/ja9047398. View

18.

Rocchigiani L, Fernandez-Cestau J, Agonigi G, Chambrier I, Budzelaar P, Bochmann M . Gold(III) Alkyne Complexes: Bonding and Reaction Pathways. Angew Chem Int Ed Engl. 2017; 56(44):13861-13865. PMC: 5698712. DOI: 10.1002/anie.201708640. View

19.

Nozaki K, Kusumoto S, Noda S, Kochi T, Chung L, Morokuma K . Why did incorporation of acrylonitrile to a linear polyethylene become possible? Comparison of phosphine-sulfonate ligand with diphosphine and imine-phenolate ligands in the Pd-catalyzed ethylene/acrylonitrile copolymerization. J Am Chem Soc. 2010; 132(45):16030-42. DOI: 10.1021/ja104837h. View

20.

Cui J, Ko H, Shing K, Deng J, Lai N, Wong M . C,O-Chelated BINOL/Gold(III) Complexes: Synthesis and Catalysis with Tunable Product Profiles. Angew Chem Int Ed Engl. 2017; 56(11):3074-3079. DOI: 10.1002/anie.201612243. View