Platinum–Carbon π-Bonded Complexes

Forniés, Juan; Lalinde, Elena

doi:10.1016/b0-08-045047-4/00107-2

Cited by 6 publications

(10 citation statements)

References 579 publications

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“…The influence of the nature of the metal (or metal-metal¢) based HOMO seems to be minimal. The presence of only the LE band at room temperature suggests that the internal conversion from the high 3 MM¢LCT excited state to the low-energy 3 p-p* is very fast at 298 K. Similar behavior is observed for complex [PtTl(bzq)(CN) 2 ], 3 which also exhibits an extended p ◊ ◊ ◊ p stacking network in solid state. However, in this complex the internal conversion between both uncoupled emissive states is relatively slow at room temperature and both bands are observed.…”

Section: Photophysical Propertiessupporting

confidence: 52%

“…The Pt-Tl bond between the corresponding filled 5d z 2 and 6s orbitals presumably causes an increase of the metal (Pt) or more probably mixed metal-metal¢ [d/s s*(Pt,Tl)] based HOMO. Therefore, this emission is attributed to a metal-metal¢-to-ligand(bzq) charge transfer MM¢LCT [d/s s*(Pt,Tl)) → p*(C∧N)] mixed, as in the precursors, with some ligand-to-ligand charge transfer (alkynyl to bzq) 3 LL¢CT.…”

Section: Photophysical Propertiesmentioning

confidence: 99%

“…Elemental analyses were carried out in a Carlo Erba EA1110 (1, 2) microanalyzer or in a Perkin-Elmer 240-B (3,4). IR spectra were recorded on a Nicolet Nexus FT (1, 2) or a Perkin-Elmer 599 (3,4) spectrophotometers (Nujol mulls between polyethylene plates). NMR spectra were recorded on a Bruker ARX-300 or a Bruker ARX-400 spectrometer, using the standard references.…”

Section: Experimental General Procedures and Materialsmentioning

confidence: 99%

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Extended structures containing Pt(ii)–Tl(i) bonds. Effect of these interactions on the luminescence of cyclometalated Pt(ii) compounds

et al. 2009

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Neutralization reactions of the appropriate precursors (NBu(4))[Pt(bzq)(C[triple bond, length as m-dash]C-R)(2)] and (NBu(4))[Pt(Cinsertion markN)(CN)(2)] (Cinsertion markN = bzq, ppy) with Tl(I) salts afford [{PtTl(bzq)(C[triple bond, length as m-dash]C-R)(2)}(2)] [R = Ph (), C(5)H(4)N-2 ()] and [PtTl(Cinsertion markN)(CN)(2)] [Cinsertion markN = bzq (), ppy ()], respectively. X-Ray diffraction studies of complexes show the existence of Pt(II)-Tl(I) bonds. In .CH(2)Cl(2) the platinum-thallium units are associated in tetranuclear Pt(2)Tl(2) entities which generate a 3-D network through short Tlpi(2-py) and pipi(bzq) contacts and additional weak Cl(2)HC-Hpi(C[triple bond, length as m-dash]C) nonclassical interactions. Compounds and show extended 2-D networks by connection of the organometallic "PtTl(Cinsertion markN)(CN)(2)" units, through secondary TlN[triple bond, length as m-dash]C contacts and moderate pipi(bzq) interactions in the case of . Complexes containing the bzq group exhibit in the solid state "luminescence thermochromism" associated to dual emission. At room temperature they show an intense, visible orange (: lambda(max) 625 nm), orange-red (: lambda(max) 640 nm) or yellow (: lambda(max) 582 nm) luminescence that changes to yellowish-green (: lambda(max) 532 nm) or green [: lambda(max) 524 nm; : lambda(max) 512 nm] upon cooling to 77 K. The unstructured low energy (LE) bands attributed to (3)pi-pi* excimeric emissions due to extensive pi-pi interactions are dominant at room temperature. By contrast, the high energy (HE) bands are highly structured and predominant at 77 K. Due to the presence of Pt-Tl bonds these HE emissions are bathochromically shifted in relation to the precursors' ones and have been tentatively assigned to a metal-metal'-to-ligand (bzq) charge transfer MM'LCT [d/s sigma*(Pt,Tl) -->pi*(Cinsertion markN)] mixed, as in the corresponding precursors, with some intraligand (3)IL[pi(Cinsertion markN') -->pi*(Cinsertion markN)] in and or ligand-to-ligand charge transfer (alkynyl to bzq) (3)LL'CT in complexes and . Complex [PtTl(ppy)(CN)(2)] , which does not show short contacts between the phenylpyridinate groups in solid state, only shows the HE green structured band both at 298 K and at 77 K. Only the cyanide derivatives are soluble and both spectroscopic (NMR and UV-Vis) and emission data (MeOH, 298 K and 77 K) indicate that the Pt(II)-Tl(I) bond breaks down in solution.

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Section: Photophysical Propertiessupporting

confidence: 52%

Section: Photophysical Propertiesmentioning

confidence: 99%

Section: Experimental General Procedures and Materialsmentioning

confidence: 99%

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Extended structures containing Pt(ii)–Tl(i) bonds. Effect of these interactions on the luminescence of cyclometalated Pt(ii) compounds

et al. 2009

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“…These initial developments sparked intense investigation into this transformation, and while ample well-characterized examples of the stoichiometric addition of amines to ethylene complexes of late transition metals have been disclosed [159], advances in catalytic versions using ethylene as a substrate remains an unsolved problem.…”

Section: Hydroamination Of Ethylenementioning

confidence: 99%

Transition‐Metal‐Catalyzed Hydroamination Reactions

Schafer

Yim

Yonson

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…In the framework of platinum chemistry, the interaction of terminal alkynes with mono-or binuclear complexes has been an intense area of research in connection with their involvement in many insertion, coupling and polymerizations reactions [5][6][7][8][9][10]. On the other hand, platinum alkynyl complexes have been attracting widespread interest for several years, mainly due to their structural variety, remarkable reactivity and photophysical properties [11][12][13][14][15][16][17][18].…”

Section: Scheme 1 Reactivity Of Complex 1 With Brønsted Acidsmentioning

confidence: 99%

A Hydrido η1-Alkynyl Diplatinum Complex Obtained from a Phosphinito Phosphanido Complex and Trimethylsilylacetylene

et al. 2014

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The reaction of (trimethylsilyl)acetylene with the phosphinito phosphanido Pt(I) complex [(PHCy2)Pt(μ-PCy2){κ 2 P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) results in the protonation of the Pt-Pt bond with the formation of the bridging hydride complex [(PHCy2)(Me3SiC≡C)Pt(μ-PCy2)(μ-H) Pt(PHCy2){κP-P(O)Cy2}](Pt-Pt) (2), which was characterized by spectroscopic, spectrometric and XRD analyses. Complex 2 exhibits in the solid state at 77 K a long-lived, weak, orange emission assigned as metal-metal to ligand charge transfer (MMLCT) (L = alkynyl) due to the presence of a very short Pt···Pt distance [2.8209(2) Å]. Reaction of 2 with etherate HBF4 results in the selective protonation of the phosphinito ligand to afford the species [(PHCy2)(Me3SiC≡C)Pt(μ-PCy2)(μ-H) Pt(PHCy2){κP-P(OH)Cy2}](Pt-Pt)[BF4] ([3]BF4).

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Platinum–Carbon π-Bonded Complexes

Cited by 6 publications

References 579 publications

Extended structures containing Pt(ii)–Tl(i) bonds. Effect of these interactions on the luminescence of cyclometalated Pt(ii) compounds

Extended structures containing Pt(ii)–Tl(i) bonds. Effect of these interactions on the luminescence of cyclometalated Pt(ii) compounds

Transition‐Metal‐Catalyzed Hydroamination Reactions

A Hydrido η1-Alkynyl Diplatinum Complex Obtained from a Phosphinito Phosphanido Complex and Trimethylsilylacetylene

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