Mono- and bi-nuclear anionic pentafluorophenyl complexes of palladium(<scp>II</scp>) and platinum(<scp>II</scp>)

Usón, Rafael; Forniés, Juan; Martínez, Francisco; Tomás, Milagros

doi:10.1039/dt9800000888

Cited by 139 publications

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“…[17][18][19] The most relevant IR absorptions are gathered in Table 1. The so-called X-sensitive vibrations [20] were assigned weak but well-defined bands in the appropriate frequency region for each type of perhalophenyl ligand.…”

Section: Resultsmentioning

confidence: 99%

“…They have also been found to undergo thermal decomposition, both in solution and in the solid state, giving rise to the corresponding C 6 X 5 ÀC 6 X 5 coupling compounds. The thermal decomposition of 3 has been followed by IR (solid state) and 19 F NMR (solution) spectroscopy. As complex 3 is consumed, concomitant formation of C 6 F 5 À C 6 F 5 and 1 in equimolar amounts is observed.…”

Section: Resultsmentioning

confidence: 99%

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Homoleptic Organoderivatives of High‐Valent Nickel(III)

Alonso

Arauzo

García‐Monforte

et al. 2009

Chemistry A European J

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Homoleptic perhalophenyl derivatives of divalent nickel complexes with the general formula [NBu(4)](2)[Ni(II)(C(6)X(5))(4)] [X=F (1), Cl (2)] have been prepared by low-temperature treatment of the halo-complex precursor [NBu(4)](2)[NiBr(4)] with the corresponding organolithium reagent LiC(6)X(5). Compounds 1 and 2 are electrochemically related by reversible one-electron exchange processes with the corresponding organometallate(III) compounds [NBu(4)][Ni(III)(C(6)X(5))(4)] [X=F (3), Cl (4)]. The potentials of the [Ni(III)(C(6)X(5))(4)](-)/[Ni(II)(C(6)X(5))(4)](2-) couples are +0.07 and -0.11 V for X=F or Cl, respectively. Compounds 3 and 4 have also been prepared and isolated in good yield by chemical oxidation of 1 or 2 with bromine or the amminium salt [N(C(6)H(4)Br-4)(3)][SbCl(6)]. The [Ni(III)(C(6)X(5))(4)](-) species have SP-4 structures in the salts 3 and 4, as established by single-crystal X-ray diffraction methods. The [Ni(II)(C(6)F(5))(4)](2-) ion in the parent compound 1 has also been found to exhibit a rather similar SP-4 structure. According to their SP-4 geometry, the Ni(III) compounds (d(7)) behave as S=1/2 systems both at microscopic (EPR) and macroscopic levels (ac and dc magnetization measurements). The spin Hamiltonian parameters obtained from the analysis of the magnetic behavior of 3 and 4 within the framework of ligand field theory show that the unpaired electron is centered mainly on the metal atom, with >97 % estimated d(z(2) ) contribution. Thermal decomposition of 3 and 4 proceeds with formation of the corresponding C(6)X(5)--C(6)X(5) coupling compounds.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Homoleptic Organoderivatives of High‐Valent Nickel(III)

Alonso

Arauzo

García‐Monforte

et al. 2009

Chemistry A European J

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“…The acetylenes were purchased and used without further purification. [PtCl 2 (tht) 2 ] [89] and (NBu 4 ) 2 [Pt(CCR) 4 ] [57] (R = 4-CH 3 C 6 H 4 , 4-CF 3 C 6 H 4 ) were prepared as described previously.…”

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confidence: 99%

Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η²(π⋅⋅⋅Tl)‐Bonding Interactions

Berenguer

Forniés

Gil

et al. 2006

Chemistry A European J

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A novel series of [PtTl(2)(C[triple chemical bond]CR)(4)](n) (n = 2, R = 4-CH(3)C(6)H(4) (Tol) 1, 1-naphthyl (Np) 2; n = infinity, R = 4-CF(3)C(6)H(4) (Tol(F)) 3) complexes has been synthesized by neutralization reactions between the previously reported [Pt(C[triple chemical bond]CR)(4)](2-) (R = Tol, Tol(F)) or novel (NBu(4))(2)[Pt(C[triple chemical bond]CNp)(4)] platinum precursors and Tl(I) (TlNO(3) or TlPF(6)). The crystal structures of [Pt(2)Tl(4)(C[triple chemical bond]CTol)(8)]4 acetone, 14 acetone, [Pt(2)Tl(4)(C[triple chemical bond]CNp)(8)]3 acetone1/3 H(2)O, 23 acetone 1/3 H(2)O and [[PtTl(2)(C[triple chemical bond]CTol(F))(4)](acetone)S](infinity) (S = acetone 3 a; dioxane 3 b) have been solved by X-ray diffraction studies. Interestingly, whereas in the tolyl (1) and naphthyl (2) derivatives, the thallium centers exhibit a bonding preference for the electron-rich alkyne entities to yield crystal lattices based on sandwich hexanuclear [Pt(2)Tl(4)(C[triple chemical bond]CR)(8)] clusters (with additional Tlacetone (1) or Tlnaphthyl (2) secondary interactions), in the C(6)H(4)CF(3) (Tol(F)) derivatives 3 a and 3 b the basic Pt(II) center forms two unsupported Pt-Tl bonds. As a consequence 3 a and 3 b form an extended columnar structure based on trimetallic slipped PtTl(2)(C[triple chemical bond]CTol(F))(4) units that are connected through secondary Tl(eta(2)-acetylenic) interactions. The luminescent properties of these complexes, which in solution (blue; CH(2)Cl(2) 1,2; acetone 3) are very different to those in solid state (orange), have been studied. Curiously, solid-state emission from 1 is dependent on the presence of acetone (green) and its crystallinity. On the other hand, while a powder sample of 3 is pale yellow and displays blue (457 nm) and orange (611 nm) emissions, the corresponding pellets (KBr, solid) of 3, or the fine powder obtained by grinding, are orange and only exhibit a very intense orange emission (590 nm).

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“…1630 (m), 1500 (vs), 1050 (vs), 950 (vs) and 760 (s-vs) era-1 Moreover, the presence of a single band observed for the X-sensitive mode [7] of mainly v(M-C) character in the range 800-750 cm-1 can be correlated [3,8,9] with the symmetry of the C-M-C skeleton. The spectra of compounds Pd(C6Fs)zDx, Pt(C~F~)2Dxa.5 and Pt(C6F~)2Dx exhibit a single band at 760, 765 and 765 era-1, respectively, as expected for the v(M-C) stretching mode of trans isomers (D~): B2u.…”

Section: Resultsmentioning

confidence: 92%

Thermal Behaviour of some dioxane adducts ofM(C6F5)2 (M=Pd, Pt)

Cutillas

Gálvez

Garcı́a

et al. 1982

Journal of Thermal Analysis

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The thermal treatment of the pentafluorophenyl derivatives M(C6Fs)eDxn [M = Pd (n = 2, 3) or Pt (n = 2); Dx = dioxane] leads to the formation of the new dioxane adducts M(C6Fs)2Dx (M = Pd, Pt) and Pt(C6Fs)2Dxl.n. Calculations of the order of reaction and the activation energy of some of the decomposition reactions are described. The values were determined by the Coats-Redfern and Freeman--Carroll methods. Structural data on the isolated intermediates were obtained by infrared spectroscopy and magnetic susceptibility measurements.In a previous paper [1 ] we described the preparation of tetrahydrofurane-dioxane solutions apparently containing Pd(CnFs) z. From these solutions, it was possible to i~olate the dioxan adducts Pd(C6Fs)2Dxn (n = 2, 3).Since the same method had been already applied to nickel [2], we extended our investigation to platinum, which we have observed also forms the adduct Pt(C6Fs)zDx 2. Moreover, the thermal treatment of the palladium and platinum compounds herein described leads to the formation of new dioxane adducts. Experimental MethodsMagnetic susceptibility was determined by the Gouy method at room temperature. IR spectra were recorded in the range 4000,--250 cm-1 on a Perkin-Elmer 457 speetrophotometer, from Nujol mulls and KBr pellets. Thermal decomposition studies (TG and DTA) were carried out in air or nitrogen on a Netzsch STA-429 thermobalance, working at the following parameters: chart speed, 120 mm/h; flow velocity of gas, 45 ml/min; heating rate, 5 deg/min. ~-A1203 was used as reference material. Samples and reference material were kept in platinum crucibles. MicroanalysesC, H analyses were performed with a Perkin-Elmer 240 microanalyzer. Palladium was determined as dimethylglyoximate [3]. Platinum was controlled by heating the samples in air at ca. 550 ~ and then weighing the residue as metallic platinum.5*

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Mono- and bi-nuclear anionic pentafluorophenyl complexes of palladium(II) and platinum(II)

Cited by 139 publications

References 0 publications

Homoleptic Organoderivatives of High‐Valent Nickel(III)

Homoleptic Organoderivatives of High‐Valent Nickel(III)

Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η²(π⋅⋅⋅Tl)‐Bonding Interactions

Thermal Behaviour of some dioxane adducts ofM(C6F5)2 (M=Pd, Pt)

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Mono- and bi-nuclear anionic pentafluorophenyl complexes of palladium(II) and platinum(II)

Cited by 139 publications

References 0 publications

Homoleptic Organoderivatives of High‐Valent Nickel(III)

Homoleptic Organoderivatives of High‐Valent Nickel(III)

Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η2(π⋅⋅⋅Tl)‐Bonding Interactions

Thermal Behaviour of some dioxane adducts ofM(C6F5)2 (M=Pd, Pt)

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Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η²(π⋅⋅⋅Tl)‐Bonding Interactions