The behavior of the tetra-υ-pyrophosphito-diplatinum(II) ion Pt2(P2O5H2)4−4 and related species

Zipp, Arden P.

doi:10.1016/0010-8545(88)80031-6

Cited by 103 publications

(85 citation statements)

References 68 publications

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“…Pt-POP is a square-planar molecule with D 4h -symmetry (figure 7a, left panel) that undergoes pronounced contraction along the metal-metal bond axis upon excitation of the 5dσ * → 6pσ electronic transition [201]. Previous reports highlighted a 3 A 2u -symmetry lowest-lying triplet state [204,205], with a measured lifetime of 9.8 µs in deoxygenated water [206][207][208] and a quantum yield of approximately 100% [208].…”

Section: (C) the Solution-phase Photochemistry Of The Transition Metamentioning

confidence: 97%

Synchrotron ultrafast techniques for photoactive transition metal complexes

Borfecchia

Garino

Salassa

et al. 2013

Phil. Trans. R. Soc. A.

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In the last decade, the use of time-resolved X-ray techniques has revealed the structure of lightgenerated transient species for a wide range of samples, from small organic molecules to proteins. Time resolutions of the order of 100 ps are typically reached, allowing one to monitor thermally equilibrated excited states and capture their structure as a function of time. This review aims at providing a general overview of the application of timeresolved X-ray solution scattering (TR-XSS) and time-resolved X-ray absorption spectroscopy (TR-XAS), the two techniques prevalently employed in the investigation of light-triggered structural changes of transition metal complexes. In particular, we herein describe the fundamental physical principles for static XSS and XAS and illustrate the theory of timeresolved XSS and XAS together with data acquisition and analysis strategies. Selected pioneering examples of photoactive transition metal complexes studied by TR-XSS and TR-XAS are discussed in depth.

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Section: (C) the Solution-phase Photochemistry Of The Transition Metamentioning

confidence: 97%

Synchrotron ultrafast techniques for photoactive transition metal complexes

Borfecchia

Garino

Salassa

et al. 2013

Phil. Trans. R. Soc. A.

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“…[6][7][8] In this field, increasing attention is currently being devoted to the construction of extended chains that are based on weak noncovalent closed-shell metal-metal bonding interactions. [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] In particular, platinum-d 8 complexes have proven to be versatile building blocks for the formation of stacked linearchain materials with short Pt···Pt contacts, [25][26][27][28][29][30] which are notably enhanced by strong-field and p-acidic ligands such as CN À or CNR. Remarkable examples include the wellknown simple, partially oxidized [Pt(CN) 4 ] n 2nÀ salts [31,32] and the double salts [Pt(CNAr) 4 ][Pt(CN) 4 ] reported recently by Mann and co-workers, [33][34][35] which display vapochromic behavior.…”

Section: Introductionmentioning

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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“…The platinum(III) binuclear complexes are structurally classified into three groups according to the number of the bridging ligands [1][2][3]: (1) four bridged ''lantern-type'' complexes coordinated by symmetric [9][10][11][12][13][14][15][16][17] or asymmetric bridging ligands [18,19] and (2) ''platinum blues''-derived amidato-bridged complexes having two bridging ligands [1][2][3][20][21][22][23][24] (Chart 1), and (3) diplatinum(III) complexes with no bridging ligand (very rare) [25,26]. Most of the complexes of group (1) and (2) are considerably stable in solid and/or in solution, and have been widely studied.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

Iwatsuki

Ishihara

Matsumoto

2006

Science and Technology of Advanced Materials

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The axial water ligand substitution reaction on the head-to-head (HH) and head-to-tail (HT) amidato-bridged cis-diammineplatinum(III) binuclear complexes, HH-and HT-[Pt 2 (NH 3 ) 4 (m-amidato) 2 (OH 2 ) 2 ] 4+ (amidato ¼ a-pyridonato, a-pyrrolidonato, or pivalamidato), with halide ions (X À ¼ Cl À , Br À ) in acidic aqueous solution reveals a consecutive 2-step kinetics under the pseudo first-order conditions of a large excess concentration of halide ion relative to that of the complex ðC X À bC Pt Þ, corresponding to formation of the monohalo (step 1) and the dihalo complexes (step 2). The first substitution step of all the HH and HT diaqua dimers consists of two parallel reaction pathways: one is the simple substituion path of one of the coordinated aqua ligands with X À , and the other is the replacement in the aquahydroxo complex which is the conjugate base of the diaqua dimer. In step 2, there are three reaction pathway patterns: the direct substitution path, the path via a coordinatively unsaturated intermediate, and the unusual path of OH À replacement.Step 2 proceeds via either one or two paths of the three depending on the nature of the halide ion as well as the bridging ligand. On the other hand, the substitution reaction of the hydrogenphosphato-bridged lantern-type complex, [Pt 2 (m-HPO 4 ) 4 (OH 2 ) 2 ] 2À proceeds in 1-step at C X À bC Pt , in which the first aqua ligand substitution to form the monohalo species is rate-determining and the monohalo species is in rapid equilibrium with the dihalo complex. The rate-determining step consists of parallel pathways similar to step 1 in the amidato-bridged complex systems. r

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The behavior of the tetra-υ-pyrophosphito-diplatinum(II) ion Pt2(P2O5H2)4−4 and related species

Cited by 103 publications

References 68 publications

Synchrotron ultrafast techniques for photoactive transition metal complexes

Synchrotron ultrafast techniques for photoactive transition metal complexes

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

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

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The behavior of the tetra-υ-pyrophosphito-diplatinum(II) ion Pt2(P2O5H2)4−4 and related species

Cited by 103 publications

References 68 publications

Synchrotron ultrafast techniques for photoactive transition metal complexes

Synchrotron ultrafast techniques for photoactive transition metal complexes

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

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

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Product

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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