[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/ange.201101231

Cited by 17 publications

(10 citation statements)

References 76 publications

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“…In other words, the carbonyl is easily dissociated from intact OC:···Au···:CF 3 .T his simple estimation explains the experimentalr esult that the CO molecule can be readily replaced by other ligands in OC···AuÀ CF 3 ,w hich has been established as av aluables ynthon of the "AuCF 3 "f ragment. [25] …”

Section: C/4e Hyperbondingmentioning

confidence: 97%

“…Thus,herein, we investigated interactions in the complete set of B···MÀX( B= CO, H 2 O, H 2 S, C 2 H 2 ,C 2 H 4 ;M= Cu, Ag, Au;X= F, Cl, Br) complexes throughq uantum chemical calculations. In addition, two other coinage metal carbonyl series (OC···MÀCH 3 and OC···MÀCF 3 )w ere also studied because of the symmetry-imposed linear OC···MÀCa rrangement.A mong them, the gold carbonyl compound OC···AuÀCF 3 was reported by Fornies et al, [25] and suggested to be ah ighly reactive intermediate speciesi nw hich CO could be readily replaced by an umber of other ligands. The methyl derivativeO C···AuÀCH 3 has not yet been prepared, but is predicted to be substantially less stable than OC···AuÀCF 3 .I na ddition to the basic bonding situation, we want to understand the influence of substituent atom/group Xo nm odulating the OC···M bond strength for the OC···MÀXseries.…”

Section: Introductionmentioning

confidence: 95%

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Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH₃, CF₃) Complexes

et al. 2015

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The resonance character of Cu/Ag/Au bonding is investigated in B⋅⋅⋅M-X (M=Cu, Ag, Au; X=F, Cl, Br, CH3, CF3; B=CO, H2O, H2S, C2H2, C2H4) complexes. The natural bond orbital/natural resonance theory results strongly support the general resonance-type three-center/four-electron (3c/4e) picture of Cu/Ag/Au bonding, B:M-X↔B(+) -M:X(-) , which mainly arises from hyperconjugation interactions. On the basis of such resonance-type bonding mechanisms, the ligand effects in the more strongly bound OC⋅⋅⋅M-X series are analyzed, and distinct competition between CO and the axial ligand X is observed. This competitive bonding picture directly explains why CO in OC⋅⋅⋅Au-CF3 can be readily replaced by a number of other ligands. Additionally, conservation of the bond order indicates that the idealized relationship bB⋅⋅⋅M +bMX =1 should be suitably generalized for intermolecular bonding, especially if there is additional partial multiple bonding at one end of the 3c/4e hyperbonded triad.

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Section: C/4e Hyperbondingmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 95%

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH₃, CF₃) Complexes

et al. 2015

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“…This hydrolytic process represents an excellent way to obtain nearly monodispersed gold nanoparticles with the advantages of the simplicity of the transformation and the possibility of attaining chemical control of the decomposition kinetics 132. The CF 3 AuCO intermediate (Figure 10) was later obtained by low‐temperature treatment of the homoleptic [Au(CF 3 ) 2 ] 2– with BF 3 · Et 2 O in CH 2 Cl 2 133. In this reaction the transient difluorocarbene species was not detected; it could possibly be stabilized by coordination of a Et 2 O molecule, which might also be crucial in accomplishing the transformation of the CF 2 fragment into the CO unit by acting as the oxygen source (Scheme ).…”

Section: Formation Of Difluorocarbenesmentioning

confidence: 99%

The Trifluoromethyl Group in Transition Metal Chemistry

2012

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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%

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

Cited by 17 publications

References 76 publications

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH₃, CF₃) Complexes

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH₃, CF₃) Complexes

The Trifluoromethyl Group in Transition Metal Chemistry

Gold(I) and Gold(III) Trifluoromethyl Derivatives

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

Cited by 17 publications

References 76 publications

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH3, CF3) Complexes

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH3, CF3) Complexes

The Trifluoromethyl Group in Transition Metal Chemistry

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Contact Info

Product

Resources

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

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH₃, CF₃) Complexes

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH₃, CF₃) Complexes