Rational synthesis of di-, tri- and tetranuclear compounds by using the [Pt(C6F5)2(C5H4NS)]− anion as a metalloligand

Falvello, Larry R.; Forniés, Juan; Fortuño, Consuelo; Gómez‐Saso, Miguel A.; Menjón, Babil; Rueda, A.; Tomás, Milagros

doi:10.1016/s0020-1693(97)05681-8

Cited by 10 publications

(5 citation statements)

References 17 publications

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“…The Pt atom is in a nearly square-planar environment. The Pt(1)−S(1) distance (2.371(3) Å) is very similar to that found in complex 10 and in other related complexes . The coordination of the Au centers to the S and P atoms can be considered as quasi-linear (P(3)−Au(2)−S(1) = 176.81 (12)° and P(2)−Au(1)−S(1) = 170.55 (11)°).…”

Section: Resultssupporting

confidence: 76%

“…The Pt atom is in a nearly square-planar environment, whereas the geometry around Ag deviates from linearity; the angle P(2)−Ag(1)−S(1) is 167.05 (6)°. In the related complex [Pt(C 6 F 5 ) 2 (PPh 3 )(C 5 H 4 NS)AgPPh 3 ], in which the Pt II and Ag I centers are linked by the bridging S atom of the pyridine-2-thiolato ligand, the geometry around Ag can be considered to be quasi-linear 175.71(9)°. The Pt(1)−S(1) distance in complex 10 (2.3617 (12) Å) is very similar to that found in [Pt(C 6 F 5 ) 2 (PPh 3 )(C 5 H 4 NS)AgPPh 3 ] .…”

Section: Resultsmentioning

confidence: 99%

“…In the related complex [Pt(C 6 F 5 ) 2 (PPh 3 )(C 5 H 4 NS)AgPPh 3 ], in which the Pt II and Ag I centers are linked by the bridging S atom of the pyridine-2-thiolato ligand, the geometry around Ag can be considered to be quasi-linear 175.71(9)°. The Pt(1)−S(1) distance in complex 10 (2.3617 (12) Å) is very similar to that found in [Pt(C 6 F 5 ) 2 (PPh 3 )(C 5 H 4 NS)AgPPh 3 ] . The Ag(1)····Pt(1) distance (3.366(1) Å) is too long to be considered a bonding interaction.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu₄]₂[{Pt(C₆F₅)₂(μ-SH)}₂], [Pt(C₆F₅)₂(PPh₃){S(H)AgPPh₃}], and [Pt(C₆F₅)₂(PPh₃){S(AuPPh₃)₂}]

et al. 2001

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The reactions of the hydroxo complexes [M(2)R(4)(mu-OH)(2)](2)(-) (M = Pd, R = C(6)F(5), C(6)Cl(5); M = Pt, R = C(6)F(5)), [[PdR(PPh(3))(mu-OH)](2)] (R = C(6)F(5), C(6)Cl(5)), and [[Pt(C(6)F(5))(2)](2)(mu-OH)(mu-pz)](2-) (pz = pyrazolate) with H(2)S yield the corresponding hydrosulfido complexes [M(2)(C(6)F(5))(4)(mu-SH)(2)](2-), [[PdR(PPh(3))(mu-SH)](2)], and [[Pt(C(6)F(5))(2)](2)(mu-SH)(mu-pz)](2-), respectively. The monomeric hydrosulfido complexes [M(C(6)F(5))(2)(SH)(PPh(3))](-) (M = Pd, Pt) have been prepared by reactions of the corresponding binuclear hydrosulfido complexes [M(2)(C(6)F(5))(4)(mu-SH)(2)](2-) with PPh(3) in the molar ratio 1:2, and they can be used as metalloligands toward Ag(PPh(3))(+) to form the heterodinuclear complex [(C(6)F(5))(2)(PPh(3))[S(H)AgPPh(3)]], and toward Au(PPh(3))(+) yielding the heterotrinuclear complexes [M(C(6)F(5))(2)(PPh(3))[S(AuPPh(3))(2)]]. The crystal structures of [NBu(4)](2)[[Pt(C(6)F(5))(2)(mu-SH)](2)], [Pt(C(6)F(5))(2)(PPh(3))[S(H)AgPPh(3)]], and [Pt(C(6)F(5))(2)(PPh(3))[S(AuPPh(3))(2)]] have been established by X-ray diffraction and show no short metal-metal interactions between the metallic centers.

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Section: Resultssupporting

confidence: 76%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu₄]₂[{Pt(C₆F₅)₂(μ-SH)}₂], [Pt(C₆F₅)₂(PPh₃){S(H)AgPPh₃}], and [Pt(C₆F₅)₂(PPh₃){S(AuPPh₃)₂}]

et al. 2001

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“…The splitting is caused by the coupling with the Ag center, and the coupling constant value is around 700 Hz (see Section 4), consistent with the existence of a Ag-P bond [77]. The low resolution of the signals does not the coupling caused by the two silver NMR active isotopes ( 107 Ag, 51.8% abundance and 109 Ag, 48.2% abundance) to be distinguished.…”

Section: Reactivity Of 1-3 Toward [Ag(oclo 3 )(Pph 3 )]supporting

confidence: 63%

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Baya

Belío

Forniés

et al. 2015

Inorganica Chimica Acta

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Luminescent complexes a b s t r a c t Complexes [Pt(C 6 F 5 )(bzq)(CNR)] {R = t Bu (1), 2-naphthyl (2), 2,6-Me 2 Ph (3)} have been prepared by replacement of the labile acetone in [Pt(C 6 F 5 )(bzq)(Me 2 CO)] with the corresponding isocyanide ligand. The structures 1 and 3 (X-ray) confirms their square planar geometry, with the bzq ligand coplanar to the metal plane. The reactions of 1-3 toward AgClO 4 lead to the trinuclear complexes [{Pt(C 6 F 5 ) (bzq)(CNR)} 2 Ag]ClO 4 {R = t Bu (4), 2-naphthyl (5)} or the tetranuclear [{Pt(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph) Ag} 2 ](ClO 4 ) 2 (6). The structures of these three polynuclear complexes have been established by X-ray diffraction studies. Two pseudo-polymorphs of 4 (4a and 4b), only differing in the crystallization solvent, have been found. 4a/b and 5 are trinuclear Pt-Ag-Pt complexes with a ''sandwich'' disposition. In all three cases, two ''Pt(C 6 F 5 )(bzq)(CNR)'' fragments are linked by a silver atom through Pt ? Ag bonds of donor acceptor nature and the silver center establishes a short g 1 interaction with the C ipso of the bzq ligands. Furthermore, the study of the structure of 6 reveals two ''(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph)PtAg'' subunits, each containing a Pt ? Ag bond related by an inversion center and held together through g 2 interactions established by the silver atom of one unit and one of the aromatic rings of the bzq ligand of the other. The reaction of 1-3 with [Ag(OClO 3 )(PPh 3 )] produces [(C 6 F 5 )(bzq)(CNR)PtAg(PPh 3 )]ClO 4 {R = t Bu, (7), 2-naphthyl (8), 2,6-Me 2 Ph (9)}. These dinuclear clusters contain a Pt ? Ag bond and show dynamic processes in solution (NMR) which involve the rupture and formation of these interactions. The X-ray structure of 7 confirms the presence of a Pt-Ag bond and a g 1 interaction with the C ipso of the bzq ligand (2.514(6) Å). All the crystal structures determined show pÁ Á Áp interactions of the bzq which stack in a parallel fashion with interplanar distances of ca. 3.3-3.4 Å. In 5 and 6 the aromatic fragments of the isocyanide ligands also take part in these pÁ Á Áp interactions. Absorption and emission properties of all the complexes 1-9 have been studied and explained with the aid of TD-DFT theoretical calculations.Compounds 1-9 are not emissive in solution but they are in rigid matrix. In glassy 2-Me-THF or CH 2 Cl 2 at 77 K the Pt/Ag compounds 4-9 at any concentration (10 À3 M, 10 À4 M, 10 À5 M) show the same emission spectra as their corresponding starting complexes 1-3, in line with the rupture of the Pt-Ag bonds. In the solid state only the dinuclear compounds [Pt(C 6 F 5 )(bzq)(CN-t Bu)AgPPh 3 ]ClO 4 (7) and [Pt(C 6 F 5 )(bzq) (CN-2,6-Me 2 Ph)AgPPh 3 ]ClO 4 (9) together with the tetranuclear complex [{Pt(C 6 F 5 )(bzq)(CN-2,6-Me 2 Ph) Ag} 2 ](ClO 4 ) 2 (6) are emissive at room temperature showing bright greenish (7, 9) or yellowish (6) phosphorescence. In all three compounds a significant contribution of M 0 orbitals (AgPPh 3 /Ag) to the frontier orbitals (FO) has been observed, and their main emissions see...

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“…Heterobimetallic compounds 24 Molecules with short /Miramolecular Pt Pt contacts are formed using bridging anions like X", RO", RS" or RSe" (R = H, alky I or aryl), [48][49][50][51][52][53][54][55][56] small nitrogen containing bridging ligands like pyrazolato, 57 amidinato or triazenido. 58,59 Also new complexes with alkinyl or phosphinoalkyne bridging ligands, 60 " 62 bidentate phosphines like dppm (dppm = bis(diphenylphosphino)methane) 63 64 or the well studied phosphonates have been reported.…”

Section: Introductionmentioning

confidence: 99%

Special Issue on Platinum Group Chemistry, Part 1:* Electronic Structure of Binuclear Platinum Complexes

Klein¹

2000

Reviews in Inorganic Chemistry

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283 1. Introduction 283 2. Electrochemistry 288 3. ESR spectroscopy 293 4. Optical spectroscopy 294 5. UV/Vis/NIR spectroelectrochemistry 296 6. Conclusion 298 7. References 299ABSTRACT Reports on investigations on the electronic structure of binuclear platinum complexes were reviewed over the past decade, focusing on compounds with organic bridging ligands that separate the metal centers but are potentially able to mediate metal-metal interaction.

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Rational synthesis of di-, tri- and tetranuclear compounds by using the [Pt(C6F5)2(C5H4NS)]− anion as a metalloligand

Cited by 10 publications

References 17 publications

Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu₄]₂[{Pt(C₆F₅)₂(μ-SH)}₂], [Pt(C₆F₅)₂(PPh₃){S(H)AgPPh₃}], and [Pt(C₆F₅)₂(PPh₃){S(AuPPh₃)₂}]

Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu₄]₂[{Pt(C₆F₅)₂(μ-SH)}₂], [Pt(C₆F₅)₂(PPh₃){S(H)AgPPh₃}], and [Pt(C₆F₅)₂(PPh₃){S(AuPPh₃)₂}]

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Special Issue on Platinum Group Chemistry, Part 1:* Electronic Structure of Binuclear Platinum Complexes

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Rational synthesis of di-, tri- and tetranuclear compounds by using the [Pt(C6F5)2(C5H4NS)]− anion as a metalloligand

Cited by 10 publications

References 17 publications

Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu4]2[{Pt(C6F5)2(μ-SH)}2], [Pt(C6F5)2(PPh3){S(H)AgPPh3}], and [Pt(C6F5)2(PPh3){S(AuPPh3)2}]

Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu4]2[{Pt(C6F5)2(μ-SH)}2], [Pt(C6F5)2(PPh3){S(H)AgPPh3}], and [Pt(C6F5)2(PPh3){S(AuPPh3)2}]

Neutral benzoquinolate cyclometalated platinum(II) complexes as precursors in the preparation of luminescent Pt–Ag complexes

Special Issue on Platinum Group Chemistry, Part 1:* Electronic Structure of Binuclear Platinum Complexes

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Product

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Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu₄]₂[{Pt(C₆F₅)₂(μ-SH)}₂], [Pt(C₆F₅)₂(PPh₃){S(H)AgPPh₃}], and [Pt(C₆F₅)₂(PPh₃){S(AuPPh₃)₂}]

Synthesis and Reactivity of Bridging and Terminal Hydrosulfido Palladium and Platinum Complexes. Crystal Structures of [NBu₄]₂[{Pt(C₆F₅)₂(μ-SH)}₂], [Pt(C₆F₅)₂(PPh₃){S(H)AgPPh₃}], and [Pt(C₆F₅)₂(PPh₃){S(AuPPh₃)₂}]