[Au(CF<sub>3</sub>)(CO)]: A Gold Carbonyl Compound Stabilized by a Trifluoromethyl Group

Martínez-Salvador, Sonia; Forniés, Juan; Martín, António; Menjón, Babil

doi:10.1002/anie.201101231

Cited by 45 publications

(52 citation statements)

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“…Herein, we report on the synthesis of new, simple salts of the homoleptic anions [Au I (CF 3 ) 2 ] − and [Au III (CF 3 ) 4 ] − together with a comparative study of their reactivity towards halogens and Lewis acids. As a result, a number of new trifluoromethyl gold(I) and gold(III) compounds have been cleanly obtained including the unusual carbonyl gold derivative [Au(CF 3 )(CO)] ( 6 ) 18. This compound, as well as the thioether complex [Au(CF 3 )(tht)] ( 10 ), are valuable synthons of the “Au(CF 3 )” unit, which, unlike its non‐fluorinated homologue Au(CH 3 ),10 has never been detected before.…”

Section: Introductionmentioning

confidence: 99%

“…As a result, a number of new trifluoromethyl gold(I) and goldA C H T U N G T R E N N U N G (III) compounds have been cleanly obtained including the unusual carbonyl gold derivative [AuA C H T U N G T R E N N U N G (CF 3 )(CO)] (6). [18] This compound, as well as the thioether complex [AuA C H T U N G T R E N N U N G (CF 3 )A C H T U N G T R E N N U N G (tht)] (10), are valuable synthons of the "AuA C H T U N G T R E N N U N G (CF 3 )" unit, which, unlike its non-fluorinated homologue AuA C H T U N G T R E N N U N G (CH 3 ), [10] has never been detected before. It is to be hoped that the availability of these convenient starting materials will stimulate a faster development of trifluoromethylgold chemistry.…”

Section: Introductionmentioning

confidence: 99%

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Gold(I) and Gold(III) Trifluoromethyl Derivatives

Martínez-Salvador

Falvello

Martín

et al. 2013

Chemistry A European J

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Trifluoromethylation of AuCl3 by using the Me3 SiCF3 /CsF system in THF and in the presence of [PPh4 ]Br proceeds with partial reduction, yielding a mixture of [PPh4 ][Au(I) (CF3 )2 ] (1') and [PPh4 ][Au(III) (CF3 )4 ] (2') that can be adequately separated. An efficient method for the high-yield synthesis of 1' is also described. The molecular geometries of the homoleptic anions [Au(I) (CF3 )2 ](-) and [Au(III) (CF3 )4 ](-) in their salts 1' and [NBu4 ][Au(III) (CF3 )4 ] (2) have been established by X-ray diffraction methods. Compound 1' oxidatively adds halogens, X2 , furnishing [PPh4 ][Au(III) (CF3 )2 X2 ] (X=Cl (3), Br (4), I (5)), which are assigned a trans stereochemistry. Attempts to activate CF bonds in the gold(III) derivative 2' by reaction with Lewis acids under different conditions either failed or only gave complex mixtures. On the other hand, treatment of the gold(I) derivative 1' with BF3 ⋅OEt2 under mild conditions cleanly afforded the carbonyl derivative [Au(I) (CF3 )(CO)] (6), which can be isolated as an extremely moisture-sensitive light yellow crystalline solid. In the solid state, each linear F3 C-Au-CO molecule weakly interacts with three symmetry-related neighbors yielding an extended 3D network of aurophilic interactions (Au⋅⋅⋅Au=345.9(1) pm). The high $\tilde \nu $CO value (2194 cm(-1) in the solid state and 2180 cm(-1) in CH2 Cl2 solution) denotes that CO is acting as a mainly σ-donor ligand and confirms the role of the CF3 group as an electron-withdrawing ligand in organometallic chemistry. Compound 6 can be considered as a convenient synthon of the "Au(I) (CF3 )" fragment, as it reacts with a number of neutral ligands L, giving rise to the corresponding [Au(I) (CF3 )(L)] compounds (L=CNtBu (7), NCMe (8), py (9), tht (10)).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Martínez-Salvador

Falvello

Martín

et al. 2013

Chemistry A European J

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“…Tyrra 59,61 These reactions probably proceed through the extremely electrophilic Au(I) difluorocarbene 109 CF 3 -AuvCF 2 , which was not detected. Tyrra 59,61 These reactions probably proceed through the extremely electrophilic Au(I) difluorocarbene 109 CF 3 -AuvCF 2 , which was not detected.…”

Section: Au(i) Trifluoromethyl Complexesmentioning

confidence: 98%

“…56,57 Since then, a relatively low number of trifluoromethyl complexes has been reported. [59][60][61] Interestingly, Au(III) complexes present a low activation barrier for the reductive elimination of R-R′ products, [62][63][64][65][66] including those with R = CF 3 . 58 It is also noteworthy that the synthetic routes to simple complexes such as [Au(CF 3 ) x ] − (x = 2, 4) have been only recently reported.…”

Section: And They Offer Industrial Applications As Advancedmentioning

confidence: 99%

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Gold trifluoromethyl complexes

Gil‐Rubio

Vicente

2015

Dalton Trans.

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This article reviews the synthesis, reactivity and applications of gold trifluoromethyl complexes, which are the only isolated perfluoroalkyl complexes of gold. The most reported examples are neutral Au(i) complexes of the type [Au(CF3)L], whereas only two Au(ii) trifluoromethyl complexes have been reported, both being diamagnetic and containing a strong Au-Au bond. A number of Au(iii) trifluoromethyl complexes have been prepared by oxidative addition of halogens or iodotrifluoromethane to Au(i) complexes or, in a few cases, by transmetallation reactions. Owing to the limitations of the available synthetic methods, a lower number of examples is known, particularly for the oxidation states (ii) and (iii). Gold trifluoromethyl complexes present singular characteristics, such as thermal stability, strong Au-C bonds and, in some cases, reactive α-C-F bonds. Some of the Au(iii) complexes reported, show unusually easy reductive elimination reactions of trifluoromethylated products which could be applied in the development of gold-catalyzed processes for the trifluoromethylation of organic compounds.

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Enhanced π‐Backdonation from Gold(I): Isolation of Original Carbonyl and Carbene Complexes

et al. 2014

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The specific electronic properties of bent o‐carborane diphosphine gold(I) fragments were exploited to obtain the first classical carbonyl complex of gold [(DPCb)AuCO]+ (ν(CO)=2143 cm−1) and the diphenylcarbene complex [(DPCb)Au(CPh2)]+, which is stabilized by the gold fragment rather than the carbene substituents. These two complexes were characterized by spectroscopic and crystallographic means. The [(DPCb)Au]+ fragment plays a major role in their stability, as substantiated by DFT calculations. The bending induced by the diphosphine ligand substantially enhances π‐backdonation and thereby allows the isolation of carbonyl and carbene complexes featuring significant π‐bond character.

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[Au(CF₃)(CO)]: A Gold Carbonyl Compound Stabilized by a Trifluoromethyl Group

Cited by 45 publications

References 75 publications

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Gold trifluoromethyl complexes

Enhanced π‐Backdonation from Gold(I): Isolation of Original Carbonyl and Carbene Complexes

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[Au(CF3)(CO)]: A Gold Carbonyl Compound Stabilized by a Trifluoromethyl Group

Cited by 45 publications

References 75 publications

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Gold trifluoromethyl complexes

Enhanced π‐Backdonation from Gold(I): Isolation of Original Carbonyl and Carbene Complexes

Contact Info

Product

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[Au(CF₃)(CO)]: A Gold Carbonyl Compound Stabilized by a Trifluoromethyl Group