Synthesis of a Coordinatively Labile Gold(III) Methyl Complex

Venugopal, Ajay; Shaw, Anthony Peter Gordon; Törnroos, Karl W.; Heyn, Richard H.; Tilset, Mats

doi:10.1021/om200327a

Cited by 17 publications

(36 citation statements)

References 52 publications

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“…Complex 2 crystallizes with 0.7 CH 2 Cl 2 and about0 .3 molecules of ad isordered C 4 hydrocarbon.A ll three compounds display the expected squareplanar geometry.T he AuÀCa nd AuÀNd istances of the cyclometallated 2-aryl pyridine are am easure of the trans-influence exertedb yt he 2,2'-bis(dicarboranyl) ligand in gold(III) compounds. The AuÀNd istance is particularly sensitive to such effects ( Figure 1), and comparison of these distances with those of other examples of the type (C^N)Au(X)(Y), where Xa nd Y are ligands from different positions in the spectrochemical series such as Me > aryl > trifluoroacetate > Cl À > triflate, [37][38][39][40] allows an evaluation of the electronic effect of the bis(dicarboranyl) ligand.…”

Section: Resultsmentioning

confidence: 99%

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Chambrier

Hughes

Jeans

et al. 2020

Chemistry A European J

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The reaction of 1,1'-Li 2 [(2,2'-C 2 B 10 H 10 ) 2 ]w ith the cyclometallated gold(III) complex( C^N)AuCl 2 afforded the first examples of gold(III) dicarboranyl complexes. The reactivity of these complexes is subject to the trans-influence exerted by the dicarboranyl ligand,w hichi ss ubstantially weaker than that of non-carboranyl anionic C-ligands. In line with this, displacemento fc oordinated pyridine by chloride is only possible under forcing conditions. While treatment of (C^N)Au{(2,2'-C 2 B 10 H 10 ) 2 }( 2)w ith triflic acid leads to AuÀC rather than AuÀNb ond protonolysis, aqueous HBr cleaves the AuÀNb ond to give the pyridinium bromo complex 7.The trans-influence of as eries of ligands including dicarboranyl and bis(dicarboranyl) was assessed by meansofD FT calculations. The analysis demonstrated that it was not suffi-cient to rely exclusively on geometricd escriptors (calculated or experimental) when attempting to rank ligands fort heir trans influence. Complex( C^N)Au(C 2 B 10 H 11 ) 2 containing two non-chelating dicarboranyll igandsw as prepared similar to 2.I ts reaction with trifluoroacetic acida lso leads to AuÀN cleavage to give trans-(Hpy^C)Au(OAc F )(C 2 B 10 H 11 ) 2 (8). In crystals of 8 the pyridiniumN ÀHb ond points towards the metal centre, while in 7 it is bent away.T he possible contribution of gold(III)···HÀNh ydrogen bonding in these complexes was investigated by DFT calculations. The results show that, unlike the situation for platinum(II), there is no evidencef or an energeticallys ignificant contribution by hydrogen bonding in the case of gold(III).

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Section: Resultsmentioning

confidence: 99%

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Chambrier

Hughes

Jeans

et al. 2020

Chemistry A European J

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“…(dmp = 2-(dimethylaminomethyl)phenyl, NC 9 H 6 O = 8-hydroxyquinoline) [25]. For square planar gold(III) complexes with more spatial ligands such as PPh 3 the interaction of the counter-anion with the gold center is sterically hindered as in [AuCl(CH 3 )(tpy)]SO 3 CF 3 (tpy = 2-p-tolylpyridine) [26]. It is interesting to observe these multiple contacts of the polyatomic counter anions BF 4 -and SO 3 CF 3 -with the terpyridine ligand of the complex cation [AuCl(terpy)] 2?…”

Section: Resultsmentioning

confidence: 99%

Crystal Structure Analysis of Two Chloro(2,2′:6′,2″-terpyridine)gold(III) Complexes

2012

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The X-ray crystal structure analysis of [AuCl-(terpy)](BF 4 ) 2 and [AuCl(terpy)](SO 3 CF 3 ) 2 show with the counter anions BF 4 -and SO 3 CF 3 -an expanded, more or less distorted octahedral coordination geometry. These secondary bonding interactions of the counter anions with the square planar complex cation [AuCl(terpy)] 2? are discussed and compared with those found in related gold(III) terpyridine complexes. In [AuCl(terpy)](SO 3 CF 3 ) 2 a very short non-bonding Au-O distance of 2.7641(4)Å of one of the triflate ions was found. The tetrafluoroborate complex is monoclinic with space group P2 1 / c and cell parameters a = 8.7587 (12)Å , b = 13.2623(19)Å , c = 15.537(2)Å , b = 90.362(2)°, V = 1804.7(4)Å 3 , Z = 4. The triflate complex is triclinic with space group P " 1 and cell parameters a = 7.4198(15)Å , b = 12.069(2)Å , c = 13.583(3)Å , a = 101.414(3)°, b = 101.922(3)°, c = 94.838(4)°, V = 1156.6(4)Å 3 , Z = 2.

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“…The unobserved cationic ethylene complex 6 is generated from either 1 or 2, in agreement with our previous findings. The hydroxyethyl complex 7 is an analogue of Au(tpy)Me(OTf ) and Au(tpy)Me(OAc); both have been structurally characterized as the pertinent stereoisomers with Me trans to N. 24 Complex 8 is closely related to [Au(tpy)Me(NCMe)][BF 4 ] (9) which has been prepared with the relevant stereochemistry at Au by bromide abstraction from AuBrMe(tpy) with AgBF 4 in acetonitrile. 11 Acetonitrile substitution for the − OAc F anion of 7 at the kinetically most accessible position 11 trans to tpy-C furnishes a crucial intermediate 8, which undergoes cyclization by an intramolecular nucleophilic attack of the hydroxyethyl-O atom on the nitrile-C atom of acetonitrile, analogous to the alcoholysis of Pt(II)-coordinated nitriles to provide Pt(II) imino ethers.…”

Section: Mechanistic Studies By Experiments and Dft Calculationsmentioning

confidence: 99%

Small-molecule activation at Au(iii): metallacycle construction from ethylene, water, and acetonitrile

et al. 2016

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Incorporation of the simple, readily available, building blocks ethylene, water and acetonitrile into Au(tpy)(OCOCF3)2 (tpy = 2-(p-tolyl)pyridine) in a one-step reaction leads to high yields of a new 6-membered ring gold(iii) metallacycle complex. The metallacycle has been characterized spectroscopically and crystallographically, and the mechanism of its formation has been investigated with the aid of DFT calculations.

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Synthesis of a Coordinatively Labile Gold(III) Methyl Complex

Cited by 17 publications

References 52 publications

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Crystal Structure Analysis of Two Chloro(2,2′:6′,2″-terpyridine)gold(III) Complexes

Small-molecule activation at Au(iii): metallacycle construction from ethylene, water, and acetonitrile

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Synthesis of a Coordinatively Labile Gold(III) Methyl Complex

Cited by 17 publications

References 52 publications

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of AuIII Dicarboranyl Chemistry

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of AuIII Dicarboranyl Chemistry

Crystal Structure Analysis of Two Chloro(2,2′:6′,2″-terpyridine)gold(III) Complexes

Small-molecule activation at Au(iii): metallacycle construction from ethylene, water, and acetonitrile

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Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry