Systematic Reactions of [Pt(PF<sub>3</sub>)<sub>4</sub>]

Drews, Thomas; Rusch, Dieter; Seidel, Stefan; Willemsen, Stefan; Seppelt, Konrad

doi:10.1002/chem.200701786

Cited by 21 publications

(24 citation statements)

References 30 publications

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“…It can also be isolated as a thermally labile, white solid in moderate yield (34 %). Given the similar properties of the PF 3 and CO molecules when acting as ligands in transition‐metal chemistry,36 there is a formal relationship between compound 6 and the trifluorophosphine derivative [Au I (CF 3 )(PF 3 )]. The latter substance was obtained by low‐temperature treatment of [AuCl(PF 3 )] with Cd(CF 3 ) 2 ⋅ dme (dme=dimethoxyethane), but it was poorly characterized due to its high sensitivity and thermal instability 37.…”

Section: Resultsmentioning

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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Section: Resultsmentioning

confidence: 99%

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Martínez-Salvador

Falvello

Martín

et al. 2013

Chemistry A European J

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“…Reactions with anhydrous HF were performed by its distillation into PFA tubes (PFA = perfluorovinylether tetrafluoroethylene copolymer) by using a stainless steel vacuum line. [13] A 300 mL stainless steel autoclave was filled with commercial PCl 3 (30 g, 218 mmol), and HF (13.8 g, 0.7 mol) was then condensed into it. Raman spectra were recorded with a Bruker RFS 100 FT Raman spectrometer.…”

Section: Methodsmentioning

confidence: 99%

“…[(F 2 PCH 2 ) 2 Pt(CH 3 ) 2 ] is formed in solution and can be identified by 1 H, 13 C, 19 F, 31 P, and 195 Pt NMR spectroscopy. Concentration of such solution results in an insoluble material that is probably polymeric.…”

Section: [(F 2 Pch 2 ) 2 Pt(ch 3 ) 2 ] and [(F 2 P) 2 Ch 2 Pt(ch 3 ) mentioning

confidence: 99%

“…clear solution was obtained by carefully warming of the suspension to 50°C. 31 P NMR (CDCl 3 ): δ = 192.6 (m) ppm.19 F NMR (CDCl 3 ): δ = -60.6 (m), -74.7 (m) ppm 13. The crystals were dried in high vacuum.…”

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confidence: 99%

“…Upon cooling of the solution to 5°C, yellow crystals formed. 31 P{ 19 F} NMR (-70°C): major product δ = 78.0 (s, 1 J P,Pt = 1580 Hz), 53.0 (s, 1 J P,Pt = 5600 Hz); minor product: 74.3 (s, 1 J P,Pt = 1580 Hz), 56.2 (s, 1 J P,Pt = 5300 Hz) ppm 13. Yield 400 mg (70 %).…”

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Volatile Methylplatinum Complexes – Formation and Reactions in Anhydrous HF

Friedemann

Seppelt

2012

Eur J Inorg Chem

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are obtained by ligand exchange reactions. The thermal stability of the complexes increases in the given sequence, whereas their volatility decreases. Demethylation reactions with anhydrous HF [a] 1197 cleave one methyl group. The addition of AsF 5 and SbF 5 often cleaves both methyl groups. The resulting L 2 Pt 2+ compounds are obtained in crystalline form with the corresponding [AsF 6 ] -, [SbF 6 ] -, [Sb 2 F 11 ] -, and [B 12 F 12 ] 2anions. Bridged dimeric or trimeric platinum complexes are also formed.

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Unexpected Direct Iron‐Fluorine Bonds in Trifluorophosphane Iron Complexes: An Alternative to Bridging Trifluorophosphane and Difluorophosphido Groups

Zou

Xie

et al. 2008

Chemistry A European J

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The iron trifluorophosphane complexes [Fe(PF(3))(n)] (n=4, 5), [Fe(2)(PF(3))(n)] (n=8, 9), [H(2)Fe(PF(3))(4)], and [Fe(2)(PF(2))(2)(PF(3))(6)] have been studied by density functional theory. The lowest energy structures of [Fe(PF(3))(4)] and [Fe(PF(3))(5)] are a triplet tetrahedron and a singlet trigonal bipyramid, respectively. Both cis and trans octahedral structures were found for [H(2)Fe(PF(3))(4)] with the cis isomer lying lower in energy by approximately 10 kcal mol(-1). The lowest energy structure for [Fe(2)(PF(3))(8)] has two [Fe(PF(3))(4)] units linked only by an iron-iron bond of length 2.505 A consistent with the formal Fe=Fe double bond required to give both iron atoms the favored 18-electron configuration. In the lowest energy structure for [Fe(2)(PF(3))(9)] one of the iron atoms has inserted into a P-F bond of one of the PF(3) ligands to give a structure [(F(3)P)(4)Fe<--PF(2)Fe(F)(PF(3))(4)] with a bridging PF(2) group and a direct Fe-F bond. A bridging PF(3) group is found in a considerably higher energy [Fe(2)(PF(3))(9)] structure at approximately 30 kcal mol(-1) above the global minimum. However, this bridging PF(3) group keeps the two iron atoms too far apart (approximately 4 A) for the direct iron-iron bond required to give the iron atoms the favored 18-electron configuration. The preferred structure for [Fe(2)(PF(2))(2)(PF(3))(6)] has a bridging PF(2) group, as expected. However, this bridging PF(2) group bonds to one of the iron atoms through an P-Fe covalent bond and to the other iron through an F-->Fe dative bond, leaving an uncomplexed phosphorus lone pair.

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Systematic Reactions of [Pt(PF₃)₄]

Cited by 21 publications

References 30 publications

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Volatile Methylplatinum Complexes – Formation and Reactions in Anhydrous HF

Unexpected Direct Iron‐Fluorine Bonds in Trifluorophosphane Iron Complexes: An Alternative to Bridging Trifluorophosphane and Difluorophosphido Groups

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Systematic Reactions of [Pt(PF3)4]

Cited by 21 publications

References 30 publications

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Gold(I) and Gold(III) Trifluoromethyl Derivatives

Volatile Methylplatinum Complexes – Formation and Reactions in Anhydrous HF

Unexpected Direct Iron‐Fluorine Bonds in Trifluorophosphane Iron Complexes: An Alternative to Bridging Trifluorophosphane and Difluorophosphido Groups

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Systematic Reactions of [Pt(PF₃)₄]