Synthesis of Heteronuclear Pt−Tl Complexes with Donor−Acceptor Bonds. X-ray Structures of cis-[Tl(μ2-OOCCH3)Pt(PPh3)(C6F5)2] and (NBu4)2[{Pt(C6F5)3}2{(μ2-O,μ3-O‘CCH3)Tl}2]

Usón, Rafael; Forniés, Juan; Tomás, Milagros; Garde, Raquel; Merino, Rosa I.

doi:10.1021/ic960453y

Cited by 45 publications

(25 citation statements)

References 22 publications

(27 reference statements)

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“…Analogous decreases in the 1 JPt,P values have been observed in phosphino derivatives after complexation with Tl + . 23,29,34,62 No coupling between 31 P and thallium was observed in the phosphido derivative 7, which is consistent with the finding of other authors. 18,23,29,33,34,62 In the spectrum of 8, the signal due to the P 5 atom appears as two doublets ( 107 Ag and 109 Ag isotopes, I ) 1 / 2 ) somewhat broadened at the base due to the poorly resolved coupling of P 5 with the Pt 2 atom.…”

Section: Halide Addition/abstraction In Phosphido Deriwatiwessupporting

confidence: 92%

“…Similar spectroscopic features have been observed in other complexes displaying Tl · · · F interactions. 19,22,23,27 Analogously, the 19 F NMR spectrum of 8 at room temperature shows very broad, overlapped signals with platinum satellites for the o-F atoms, which split into six signals (1:1:3:1:1:1 intensity ratio) at 183 K. The more-intense signal is broad, and some of the platinum satellites appear overlapped. In the higher field region (m-and p-F atoms) the signals due to 12 inequivalent fluorine atoms appear overlapped.…”

Section: Halide Addition/abstraction In Phosphido Deriwatiwesmentioning

confidence: 88%

“…All of these geometric parameters are in agreement with a Pt-Tl bond. [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] A noteworthy feature of this structure is the presence of o-F · · · Tl contacts, with distances Tl-F (15) ) 2.951(7) Å and Tl-F(20) ) 3.014(7) Å, which are in the range found in platinum(II) complexes containing Pt-Tl bonds, 19,22,23,27 or thallium complexes containing intra- [37][38][39][40] or intermolecular F · · · Tl contacts. 26,29,37,[41][42][43][44][45] These o-F · · · Tl contacts are also detected in solution in the 19 F NMR spectra of 5 (below).…”

Section: Halide Addition/abstraction In Phosphido Deriwatiwesmentioning

confidence: 99%

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Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates

et al. 2008

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Reaction of unsaturated (44e (-) skeleton) [PdPt 2(mu-PPh 2) 2(mu-P 2Ph 4)(R F) 4] 4 with Br (-) produces the saturated (48e (-) skeleton) complex [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 5 without any M-M' bond. Attempts to eliminate Br (-) of 5 with Ag (+) in CH 2Cl 2 as a solvent gives a mixture of [(R F) 2Pt (III)(mu-PPh 2) 2Pt (III)(R F) 2] and some other unidentified products as a consequence of oxidation and partial fragmentation. However, when the reaction of 5 with Ag (+) is carried out in CH 3CN, no oxidation is observed but the elimination of Br (-) and the formation of [(R F) 2(CH 3CN)Pt(mu-PPh 2)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 6 (46e (-) skeleton), a complex with a Pt-Pd bond, takes place. It is noteworthy that the reaction of 5 with TlPF 6 in CH 2Cl 2 does not precipitate TlBr but forms the adduct [(R F) 2PtTl(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 7 with a Pt-Tl bond. Likewise, 5 reacts with [AgOClO 3(PPh 3)] in CH 2Cl 2 forming the adduct [AgPdPt 2(mu-Br)(mu-PPh 2) 2(mu-Ph 2P-PPh 2)(R F) 4(PPh 3)] 8, which contains a Pt-Ag bond. Both adducts are unstable in a CH 3CN solution, precipitating TlBr or AgBr and yielding the unsaturated 6. The treatment of [NBu 4] 2[(R F) 2Pt(mu-PPh 2) 2Pd(mu-PPh 2) 2Pt(R F) 2] in CH 3CN with I 2 (1:1 molar ratio) at 233 K yields a mixture of 4 and 6, which after recrystallization from CH 2Cl 2 is totally converted in 4. If the reaction with I 2 is carried out at room temperature, a mixture of the isomers [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 9 and [NBu 4][(R F)(PPh 2R F)Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2) 2Pt(R F) 2] 10 are obtained. The structures of the complexes have been established on the bases of NMR data, and the X-ray structures of 5- 8 have been studied. The relationship between the different complexes has been studied.

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Section: Halide Addition/abstraction In Phosphido Deriwatiwessupporting

confidence: 92%

Section: Halide Addition/abstraction In Phosphido Deriwatiwesmentioning

confidence: 88%

Section: Halide Addition/abstraction In Phosphido Deriwatiwesmentioning

confidence: 99%

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Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates

et al. 2008

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“…Electronic characterisation—optical spectroscopy : The presence of a direct Pt−Tl bond is often associated with intense photoluminescence, with emission bands in the energy range between 316 and 678 nm 7b, 11a,11c,11d, 18. All the compounds reported in these references contain platinum( II ) and thallium( I ) ions.…”

Section: Resultsmentioning

confidence: 99%

Tl−Pt(CN)5 in the Solid State—A Multimethod Study of an Unusual Compound Containing Inorganic Wires

et al. 2001

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The crystal and molecular structure of a polycrystalline powder with a metal-metal bond and the composition TlPt(CN)5 has been determined by combining results from X-ray powder diffraction (XRD), extended X-ray absorption fine structure (EXAFS) and vibrational spectroscopic studies. The XRD data gave the tetragonal space group P4/nmm (No. 129), with a= 7.647(3), c=8.049(3) A, Z=2, and well-determined positions of the heavy metal atoms. The Pt-TI bond length in the compound is 2.627(2) A. The platinum atom coordinates four equivalent equatorial cyano ligands, with a fifth axial CN ligand and a thallium atom completing a distorted octahedral coordination geometry. The Tl-Pt(CN)5 entities are linked together in linear -NC-Pt-Tl-NC-Pt-Tl chains through the axial cyano ligand. These linear "wires" are the essential structural features and influence the properties of the compound. A three-dimensional network is formed by the four equatorial cyano ligands of the platinum atom that form bridges to the thallium atoms of neighbouring antiparallel chains. The platinum atom and the five nitrogen atoms from the bridging cyano groups form a distorted octahedron around the thallium atom. EXAFS data were recorded at the Pt and Tl L(III) edges for a more complete description of the local structure around the Pt and Tl atoms. The excessive multiple scattering was evaluated by means of the FEFF program. Raman and infrared absorption spectroscopy reveal strong coupling of the vibrational modes of the TlPt(CN)5 entities, in particular the metal-metal stretching mode, which is split into four Raman and two IR bands. Factor group theory shows that a structural unit larger than the crystallographic unit cell must be used to assign vibrational bands. Intra- and intermolecular force constants have also been calculated. The compound exhibits red luminescence at 700 +/- 3 nm in glycerol and has a corresponding excitation maximum at 240 nm. X-ray photoelectron spectra (XPS) show that the metal atoms have intermediate oxidation states, Pt3.2+ and Tl1.6-, between those in the parent Pt(II) and Tl(III) species and the decomposition products, Pt(IV) and Tl(I). The solid compound TlPt(CN)5 is stable to 520 degrees C. However in presence of water, a two-electron transfer between the metal atoms results in the cleavage of the metal-metal bond at 80 degrees C, forming a Pt(IV) pentacyanohydrate complex and a monovalent thallium ion.

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“…[24][25][26][27][28] Forniés investigated the properties of Pt II /Tl I compounds that are capable of building supramolecular chains with anionic [(C 6 F 5 ) 4 Pt(µ-Tl)] -(E) units. 29 While Ag + cations have served as unsupported bridges between monovalent Group 9 metal-ligand fragments (e.g. C, Scheme 1) [17][18][19][20]37 and other low-valent species, when Group 10 metal bases are concerned, only examples containing divalent Pt II L n fragments are known.…”

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Silver(i) and thallium(i) cations as unsupported bridges between two metal bases

et al. 2014

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Stirring Lewis-basic transition metal complexes with the salts M[BAr(Cl)4] (M = Ag, Tl; Ar(Cl) = 3,5-C6H3Cl2) resulted in the formation of diplatinum complexes [{(Cy3P)2Pt}2(μ-Ag)][BAr(Cl)4] (3) and [{(Cy3P)2Pt}2(μ-Tl)][BAr(Cl)4] (4) and the diiron compound [{(OC)3(Me3P)2Fe}2(μ-Ag)] (5) featuring bridging, unsupported metal cations. Their properties were investigated by multinuclear NMR spectroscopy, as well as X-ray diffraction and infrared measurements.

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Synthesis of Heteronuclear Pt−Tl Complexes with Donor−Acceptor Bonds. X-ray Structures of cis-[Tl(μ₂-OOCCH₃)Pt(PPh₃)(C₆F₅)₂] and (NBu₄)₂[{Pt(C₆F₅)₃}₂{(μ₂-O,μ₃-O‘CCH₃)Tl}₂]

Cited by 45 publications

References 22 publications

Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates

Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates

Tl−Pt(CN)5 in the Solid State—A Multimethod Study of an Unusual Compound Containing Inorganic Wires

Silver(i) and thallium(i) cations as unsupported bridges between two metal bases

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