Preparation of Au(I), Ag(I), and Pd(II) N-Heterocyclic Carbene Complexes Utilizing a Methylpyridyl-Substituted NHC Ligand. Formation of a Luminescent Coordination Polymer

Catalano, Vincent J.; Etogo, Anthony O.

doi:10.1021/ic070260i

Cited by 90 publications

(56 citation statements)

References 34 publications

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“…Here again, the 13 C NMR signal for the carbene carbon of 2d appeared at lower field (251.2 ppm) than that observed for 1d (235.0 ppm). (Table 1), and are in agreement with the literature for gold(I) complexes [12,[20][21][22][23][24][25][26][27][28][29][30][31]. The Au-C carbene bond lengths in 1a (1.987(9) Å) and 1b (1.983(2) Å) are comparable with those found in substituted NHC gold(I) chloro complexes [12,[18][19][20][21][22][23], and suggest a single bond character, in good agreement with the strong σ-donor character of CAACs.…”

Section: Stable Carbenes; Carbene Complexes; Goldsupporting

confidence: 90%

Cyclic (alkyl)(amino)carbene gold(I) complexes: A synthetic and structural investigation

Frey

Dewhurst

Kousar

et al. 2008

Journal of Organometallic Chemistry

127

101

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A series of mono-and dicarbene gold(I) complexes of types Au(CAAC)(Cl) [CAAC = cyclic (alkyl) (amino)carbene] (1) and [Au(CAAC) 2 ] + [X] -(X = Cl, AuCl 2 ) (2) have been prepared through reaction of AuCl(SMe 2 ) with free carbenes a-e, and structurally characterized by single X-ray diffraction studies (1a, 1b, 2d, 2e). In addition two new free cyclic (alkyl)(amino)carbenes (c and e) have been synthesized. Keywords Stable Carbenes; Carbene Complexes; GoldFollowing the discovery of the first stable derivatives [1,2], singlet carbenes have received considerable attention as ligands for transition metals [3,4]. Carbenes feature a strong σ-donating ability, and strongly bind metal centers of high and low oxidation states [5]. Additionally, the possibility to tune their electronic and steric properties by variation of substituents [6], make carbenes versatile ligands for transition metal catalysts [7]. Since the Au(I) catalyzed asymmetric aldol reaction was published in the late 1980s [8], the use of Au (I) complexes in catalysis has received a lot of attention [9,10]. The first NHC substituted neutral and cationic gold(I) complexes were published in 1989 [11], and their application in catalysis stated in 2003 [12].We have already reported the synthesis and isolation of well-defined cyclic (alkyl)(amino) carbenes (CAAC) [13a], their use for the activation of small molecules [13b-d], their properties as ligand for transition metals [13e,f], and recently the preparation of a CAAC gold(I) complex, which allows for the catalytic formation of allenes, starting from enamines and alkynes [14]. This manuscript describes the synthesis and characterization of a series of Au(I) complexes, featuring one or two CAACs, depending on the bulkiness of the carbene ligand.The free carbenes (a-e) including the new ones (c and e) were readily prepared by deprotonation with LDA of the corresponding iminium salts; the latter were synthesized using the hydroiminiumation route [15] as shown in Scheme 1.The gold complexes 1a-d were then cleanly prepared by stirring the free carbenes a-d overnight in darkness in THF with AuCl(SMe 2 ), the same procedure used for the corresponding NHC complexes [16]. After removing the solvent under vacuum and washing with hexanes, the * To whom correspondence should be addressed. E-mail: gbertran@mail.ucr.edu Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Under the same reaction conditions, a different behavior was observed for carbene e. In this case the reaction of a stoichiometric amount of e with AuCl(SMe 2 ) did not afford the expected mono-carbene gold c...

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Section: Stable Carbenes; Carbene Complexes; Goldsupporting

confidence: 90%

Cyclic (alkyl)(amino)carbene gold(I) complexes: A synthetic and structural investigation

Frey

Dewhurst

Kousar

et al. 2008

Journal of Organometallic Chemistry

127

101

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“…Eur.J. 2018,24,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] www.chemeurj.org Ferrer,R odríquez, and co-workersh ave synthesized as eries of metalloligandsc ontaining the 4-pyridyl-2,3,5,6-tetrafluorophenylu nit (tfppy). [42] By reactiono f[ Ph 3 PAu(tfppy)] with [M(OH 2 ) 2 (diphosphine)] 2 + (diphosphine = dppp, dppf;M = Pd, Pt) they isolated complexes of the type 42 ( Figure 10).…”

Section: Metalloligands Containing Pyridine Binding Sitesmentioning

confidence: 99%

“…[44] In contrast, the coordination polymer 48 crystallized after the reactiono f46 a with AgBF 4 . [45] The tetrapyridyl-substituted metalloligands (46 d-f)g ive rise to AuM 2 complexes or coordination polymers. [46] The AuCu 2 complex 49 reacts with MeOH to give complex 50.T his reaction also takes place when the solids are exposed to MeOH vapor and is reversible.…”

Section: Metalloligands Containing Pyridine Binding Sitesmentioning

confidence: 99%

“…Eur.J. 2018,24,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] www.chemeurj.org MeCN, MeOH,a nd Me 2 CO. [47] These abrupt changes in the emission energy are likely to originate from switching the Au···Cu metallophilic interactions on or off.…”

Section: Metalloligands Containing Pyridine Binding Sitesmentioning

confidence: 99%

“…2018,24,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] www.chemeurj.org to six different metal centers, such as 57,t hrough severals uccessive metalloligand-to-metal coordination steps. [53] Alkynyl-gold metalloligands containing two bipyridyl units (58)w ere reported by the groups of Chen [54] andu s ( Figure 15).…”

Section: Metalloligands Containing Pyridine Binding Sitesmentioning

confidence: 99%

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The Coordination and Supramolecular Chemistry of Gold Metalloligands

Gil‐Rubio

Vicente

2017

Chemistry A European J

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This review article deals with the use of gold metalloligands as building blocks for the assembly of heterometallic complexes.S everal families of gold complexes decorated with crown-ether, amide, pyridine, bipyridine, terpyridine, carboxylato, amino acid or p-alkyne binding sites have been reported. Adducts of these metalloligands with alkaline or transition-metal cations, or with transition-metal or lanthanide complexes, have been isolated ands tructurally characterized. The reported heterometallic species range from simple dinuclearc omplexes to self-assembled supramolecules, coordination polymers, or solids. New structuralm otifs have been found in thesec omplexes. Mosto ft hese metalloligandsa nd complexes are photoluminescent and some of them show switchable emissions based on the formation and rupture of metallophilic contacts. Potential applications as sensors, sensitizers, in vivo imaging agents, and anticancer drugs are envisaged.

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The Chemistry of Gold– NHC Carbene Complexes

Zhang

Chen

et al. 2015

Patai's Chemistry of Functional Groups

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Au‐NHC chemistry has received much attention in the last 10 years, mainly due to straightforward synthetic routes to Au(I)‐NHC complexes and their catalytic interest. Now Au‐NHC complexes have been employed, not only as highly selective catalysts in directed organic synthetic strategies, but also as dynamic intermediates to promote constructive chemical steps at the metal active center. Some very recent examples have described the stabilization imparted by NHC which allows to isolate otherwise “unstable” intermediates, such as vinylgold derivatives. Another important property shown by Au‐NHC complexes is their luminescence. The lower energy excitation and emission bands in some Au‐NHCs are of suitable wavelengths for cellular distribution studies allowing to investigate the uptake and distribution in cancer cells using fluorescence confocal microscopy. The strong Au–carbene bonds also permit stable Au‐NHC complexes immune to biologically important thiol groups, and thus Au‐NHCs have also been found to have potential in medicinal and biochemical applications.

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Preparation of Au(I), Ag(I), and Pd(II) N-Heterocyclic Carbene Complexes Utilizing a Methylpyridyl-Substituted NHC Ligand. Formation of a Luminescent Coordination Polymer

Cited by 90 publications

References 34 publications

Cyclic (alkyl)(amino)carbene gold(I) complexes: A synthetic and structural investigation

Cyclic (alkyl)(amino)carbene gold(I) complexes: A synthetic and structural investigation

The Coordination and Supramolecular Chemistry of Gold Metalloligands

The Chemistry of Gold– NHC Carbene Complexes

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