Metal derivatives of azoles. 3. The pyrazolato anion (and homologs) as a mono- or bidentate ligand: preparation and reactivity of tri-, bi-, and mononuclear gold(I) derivatives

Minghetti, Giovanni; Banditelli, Guido; Bonati, Flavio

doi:10.1021/ic50193a026

Cited by 94 publications

(26 citation statements)

References 8 publications

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“…The two-electron oxidative addition to the Au I complex [Au(CH2)-P(S)(C6Hs)2] 2 can also result in homo-or heterovalent products (Mazany & Fackler, 1984), the latter with concomitant rearrangement of the bridging ligand. The oxidation of the trinuclear complex [Au-a-{3,5-(CH3) 2-C3HN2 }]3 with 12 (Minghetti, Banditelli & Bonati, 1979) produced the heterovalent Au~/Au m species, as was suggested by its M6ssbauer spectrum (Katada et al, 1983).…”

mentioning

confidence: 88%

The structure of [Au-μ-{3,5-(C₆H₅)₂C₃HN₂}]₃Cl₂: a trinuclear mixed-valence gold pyrazolate complex

Raptis¹,

Murray²,

Fackler³

1988

Acta Crystallogr C

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mentioning

confidence: 88%

The structure of [Au-μ-{3,5-(C₆H₅)₂C₃HN₂}]₃Cl₂: a trinuclear mixed-valence gold pyrazolate complex

Raptis¹,

Murray²,

Fackler³

1988

Acta Crystallogr C

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“…Thus pyrazolato derivatives were obtained from the reaction of a diglyme solution of pyrazole complexes of copper(I1) and elemental copper (2c), or from the reaction (23) between palladium(I1) acetate and 3,5-Me2pzH (pzlH). Furthermore, even in an acid medium, that is during attempted protonation with fluoboric acid of Ph3PAu(pz17 (pz"H = 3 ,5-Me2-4-NO2-pyrazole) a proton-free dimeric cation resulted, namely [(Ph3P)Au(p-pz'7Au(PPh3)lf (1). In the absence of contrary evidence, these reactions may be written as follows:…”

Section: Resultsmentioning

confidence: 99%

“…Indeed, in thecase of copper, the published results are abundant, and include complexes with several copper (1) and copper(I1) salts (2). Other papers report the copper(I1) derivatives of various anionic or neutral substituted pyrazoles, such as polypyrazolylborates (3), bis-(1-pyrazoly1)methane (4), indazole and 5-aminoindazole ( 3 , and even the ligand (Ph2PCH2)2Pt(3,5-Me2pz-N)2 (6).…”

Section: Introductionmentioning

confidence: 99%

Metal derivatives of azoles. Part VII. Gold(I) derivatives of pyrazoles

Banditelli¹,

Bandini²,

Minghetti³

et al. 1981

Can. J. Chem.

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“…By contrast, very few related compounds containing the pyrazolato group in a monodentate fashion are known [5]. In this context, it is remarkable to note that, in previous works, the complexes [Au(PPh 3 )(pz)] (pz 3,5-dimethylpyrazolato, 3,5-dimethyl-4-nitropyrazolato) were synthesized as part of a search for polymetallic derivatives [1] [6] [7]. More recently, [Au(pz)(PPh 3 )] (pz pyrazolato) has been described and structurally characterized [8].…”

Section: Pyrazolatogold(i) Derivatives Of the Types [(Pph 3 )Au(màpz)mentioning

confidence: 99%

Pyrazolato Ligands towards Gold(I) Derivatives with Aurophilic Interactions: X-Ray Structure of Bis[3,5-(dibutoxyphenyl)-1H-pyrazolato-κN1]bis(triphenylphosphine)digold(Au⋅⋅⋅Au)([Au(pzR2)(PPh3)]2; RC4H9OC6H4)

Ovejero

Cano

Pinilla

et al. 2002

HCA

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A crossed −torch× structure and a short Au ¥¥¥ Au contact was established by X-ray analysis for the dimeric complex [Au(pz R2 )(PPh 3 )] 2 (pz R2 3,5-disubstituted pyrazolato, RC n H 2n1 ÀOÀC 6 H 4 , n 4; 1). The complex is a representative member of a new well-characterized family of derivatives containing the pyrazolato ligand in an uncommon monodentate coordination form. In addition, 1 is luminescent in the solid state at 77 K. Pyrazolatogold(I) derivatives of the types [(PPh 3 )Au(mÀpz)Au(PPh 3 )]BF 4 and [Au(mÀpz)] n (n 3, 6) [1 ± 4] have been extensively described. By contrast, very few related compounds containing the pyrazolato group in a monodentate fashion are known [5]. In this context, it is remarkable to note that, in previous works, the complexes [Au(PPh 3 )(pz)] (pz 3,5-dimethylpyrazolato, 3,5-dimethyl-4-nitropyrazolato) were synthesized as part of a search for polymetallic derivatives [1] [6] [7]. More recently, [Au(pz)(PPh 3 )] (pz pyrazolato) has been described and structurally characterized [8]. The lack of data associated with the nature of monodentate pyrazolato-containing compounds encouraged us to investigate how to produce some of these Au I derivatives.Thus, we synthesized a new family of pyrazolato complexes of the type [Au(pz R 2 )(PPh 3 )] (pz R 2 3,5-disubstituted pyrazolato R C n H 2n1 ÀOÀC 6 H 4 , n 4, 6, 8) (I) i.e., 1 ± 3. The compounds were produced by reaction of pyrazolato ligands, prepared in situ, and [AuCl(PPh 3 )] followed by addition of TlNO 3 . The thallium salt allowed us to obtain the complexes in a substantial yield after removal of TlCl. By contrast, when [AuX(PPh 3 )] (XNO 3 , CF 3 SO 3 ) were used as starting material, binuclear complexes of the type [(PPh 3 )Au(mÀpz R 2 )Au(PPh 3 )]X (II) were isolated. Based on these results, [AuCl(PPh 3 )] is proposed as the adequate parent compound to produce the pyrazolato-kN coordination to the AuPPh 3 fragment. Therefore, the nature of the AuX bond of the parent [AuX(PPh 3 )] compounds appears to be responsible for the formation either type I or type II complexes. To confirm this suggestion, repeated reactions of [AuCl(PPh 3 )] and pyrazolato ligands with subsequent addition of different silver salts like AgNO 3 , Ag(CF 3 SO 3 ), or Ag(PhCO 2 ) were carried out. In all cases, the same final products of the type [Au(pz R 2 )(PPh 3 )] (I) were obtained in high yield (Scheme).

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Metal derivatives of azoles. 3. The pyrazolato anion (and homologs) as a mono- or bidentate ligand: preparation and reactivity of tri-, bi-, and mononuclear gold(I) derivatives

Cited by 94 publications

References 8 publications

The structure of [Au-μ-{3,5-(C₆H₅)₂C₃HN₂}]₃Cl₂: a trinuclear mixed-valence gold pyrazolate complex

The structure of [Au-μ-{3,5-(C₆H₅)₂C₃HN₂}]₃Cl₂: a trinuclear mixed-valence gold pyrazolate complex

Metal derivatives of azoles. Part VII. Gold(I) derivatives of pyrazoles

Pyrazolato Ligands towards Gold(I) Derivatives with Aurophilic Interactions: X-Ray Structure of Bis[3,5-(dibutoxyphenyl)-1H-pyrazolato-κN1]bis(triphenylphosphine)digold(Au⋅⋅⋅Au)([Au(pzR2)(PPh3)]2; RC4H9OC6H4)

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Metal derivatives of azoles. 3. The pyrazolato anion (and homologs) as a mono- or bidentate ligand: preparation and reactivity of tri-, bi-, and mononuclear gold(I) derivatives

Cited by 94 publications

References 8 publications

The structure of [Au-μ-{3,5-(C6H5)2C3HN2}]3Cl2: a trinuclear mixed-valence gold pyrazolate complex

The structure of [Au-μ-{3,5-(C6H5)2C3HN2}]3Cl2: a trinuclear mixed-valence gold pyrazolate complex

Metal derivatives of azoles. Part VII. Gold(I) derivatives of pyrazoles

Pyrazolato Ligands towards Gold(I) Derivatives with Aurophilic Interactions: X-Ray Structure of Bis[3,5-(dibutoxyphenyl)-1H-pyrazolato-κN1]bis(triphenylphosphine)digold(Au⋅⋅⋅Au)([Au(pzR2)(PPh3)]2; RC4H9OC6H4)

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The structure of [Au-μ-{3,5-(C₆H₅)₂C₃HN₂}]₃Cl₂: a trinuclear mixed-valence gold pyrazolate complex

The structure of [Au-μ-{3,5-(C₆H₅)₂C₃HN₂}]₃Cl₂: a trinuclear mixed-valence gold pyrazolate complex