Oxidative addition - reductive elimination reactions of mono- and bis(aryl)platinum(II) complexes with two amino ligands in fixed trans positions. X-ray crystal structures of (2,6-bis[[dimethylamino]methyl]phenyl)(4-tolyl)platinum(IV) diiodide and (2,6-bis[[dimethylamino]methyl]phenyl)platinum(IV) trichloride

Koten, Gerard van; Terheijden, J.; Beek, Johannus A. M. van; Wehman-Ooyevaar, Icm; Müller, Felix; Stam, C. H.

doi:10.1021/om00118a003

Cited by 78 publications

(73 citation statements)

References 8 publications

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“…Comparison of the molecular structure of 11 with the earlier reported [PtCl 3 (NCN)] complex 10,13 shows a similar distorted octahedral geometry around the platinum center, containing two axial chloride atoms. The distortion of the octahedral geometry is reflected in the N-Pt-N angle of 162.35(18)-162.39(19)°a nd the small N-Pt-C ipso angles of 80.8(2)-81.6(2)°.…”

Section: Resultsmentioning

confidence: 58%

“…The platinumtoC ipso (Pt-C)distancesareintherange1.952(6)-1.957(5) Å, as expected. 10,13 Furthermore there is a significant difference between the Pt-Cl bond lengths of the two axial chloride atoms (2.3148(16)-2.3396(17) Å) and the meridonial chloride atom (2.4421(16)-2.4598(16) Å), reflecting the trans influence 17 of C ipso of the NCN fragment on the trans-Pt-Cl bond, weakening this interaction. A comparison between the molecular structure of 7 (Pt(II)), which was reported earlier, 6 and 11 (Pt(IV)) in the solid state reveals longer bonding distances of the Pt-C, Pt-N, and the Pt-Cl bonds in 11, reflecting the formal +4 oxidation state of the platinum center.…”

Section: Resultsmentioning

confidence: 99%

“…In the 13 C{ 1 H} NMR spectrum of 1 the 13 C NMR resonances of the C ipso (to platinum) carbon appeared at 146.6 ppm. The…”

Section: Resultsmentioning

confidence: 99%

“…Recently, Marder and co-workers assessed the electron-transfer-donor strengths and π-donor strengths of various amines using density functional theory calculations. 19 For the stilbenoid NCN-pincer Pt(IV)Cl 3 complex 11 the (CH 3 10,20 The same shifts are observed in the 13 C{ 1 H} NMR spectrum of 11. The largest effect is observed for C ipso , which shifts from 148.6 (in 7) to 144.9 ppm (in 11), reflecting an increase of negative charge at this atom as a result of further Pt-C bond polarization.…”

mentioning

confidence: 76%

“…[10][11][12][13] Therefore luminescent Pt(II) complex 7 was chemically oxidized, and the resulting Pt(IV) complex was studied for its physical, electronic, and solid-state properties. In order to determine the one-bond 1 J( 13 C, 195 Pt) coupling constant, which is not easy to obtain from the solution spectra, the nature of the Pt-C ipso interaction in 7 was studied using solid-state 13 C CP/MAS NMR measurements. For the fluorescent donor-acceptor stilbenoid pincer complexes 7 and 8 the application in an organic light-emitting diode (OLED) was studied.…”

Section: Introductionmentioning

confidence: 99%

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Substituted 4,4′-Stilbenoid NCN-Pincer Platinum(II) Complexes. Luminescence and Tuning of the Electronic and NLO Properties and the Application in an OLED

et al. 2008

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A series of 4,4′-disubstituted organic-organometallic stilbenes, i.e., the 4′-substituted stilbenoid-NCN-pincer platinum(II) complexes [PtCl(NCN-R-4)] (NCN-R-4 ) [C 6 H 2 (CH 2 NMe 2 ) 2 -2,6-R-4] -in which R ) C 2 H 2 C 6 H 4 -R′-4′ with R′ ) NPh 2 , NMe 2 , OMe, SiMe 3 H, I, CN, NO 2 ) (1-8), were studied for their electronic, electrochemical, and NLO properties. Complex 7 was also chemically oxidized using Cu(II)Cl 2 , yielding the [Pt(IV)Cl 3 (NCN(C 2 H 2 C 6 H 4 -CN-4′)-4)] complex 11. In contrast to 1 and 7, 11 did not show luminescent properties in solution at room temperature. In the solid state (X-ray crystallography) 11 has an overall bent structure, with the pincer moiety and the cyano group beneath the plane of the central double bond. Stilbenoid pincer complex 1 (R′ ) NPh 2 ) was also studied with UV/vis spectroscopy in a series of different solvents. The compound shows an intense low-energy transition band, appearing at a lower energy (λ max ) 374-379 nm) than 2 (R′ ) NMe 2 ), which contains a stronger donor group. The UV/vis absorption data of a selected series of stilbenoid pincer platinum complexes were interpreted in terms of a qualitative orbital model based on DFT and TD-DFT calculations. The trends observed in the transition energies correlate well with the donor/acceptor properties of the substituents. It was shown that the HOMO-LUMO gap of the stilbenoid pincer platinum compounds decreases when going from an electron-neutral group (R′ ) H) toward an electron-donating (R′ ) NMe 2 ) or -accepting (R′ ) NO 2 ) group. The fluorescence properties of 1 were also investigated using fluorescence and laser spectroscopy, showing that the metal center favors nonradiative decay from the excited state to the ground state. For 7 (R′ ) CN), solid-state 13 C CP/MAS NMR measurements were performed, and a value of 1 J( 13 C, 195 Pt) ) 1003 ( 15 Hz was obtained for the C ipso carbon, reflecting π-contributions in the carbon-metal bond. The cyclic voltammetry study on the complexes revealed an irreversible oxidation from Pt(II) to Pt(IV). In general the oxidation potential is influenced by the electronic character of the R′ substituent. The influence of the para R′ substituent on the hyperpolarizability of the compound was investigated using the femtosecond (frequencyresolved) HRS technique. For 1-7 good zzz values were measured ( zzz ranging from (164-1324) × 10 -30 esu) with the highest value for 6 (R′ ) I). The higher zzz values were found for the compounds that contain a low-energy UV/vis absorption band and/or a large absorption coefficient. Donor-acceptor complexes 7 and 8 were successfully applied in an organic light-emitting diode (OLED). In the electroluminescence spectrum of 7 (R′ ) CN) a low-energy emission band was observed at 643 nm. This band also appeared in the solid-state luminescence spectra of 7, however, only at low temperatures (298-15 K). The emission band was assigned to result from a triplet excited state. The present study shows that the introduction of a NCN-pincer platinum fragment ...

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Section: Resultsmentioning

confidence: 58%

Section: Resultsmentioning

confidence: 99%

“…In the 13 C{ 1 H} NMR spectrum of 1 the 13 C NMR resonances of the C ipso (to platinum) carbon appeared at 146.6 ppm. The…”

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 76%

Section: Introductionmentioning

confidence: 99%

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Substituted 4,4′-Stilbenoid NCN-Pincer Platinum(II) Complexes. Luminescence and Tuning of the Electronic and NLO Properties and the Application in an OLED

et al. 2008

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The First [4+2]-Coordinated Tetraorganolead Compound: Synthesis, Structure and Conversion into a Triorganolead Cation, a Benzoxaphosphaplumbole, and Diorganolead Dihalides

Peveling

Schürmann

Jurkschat

2002

Z. anorg. allg. Chem.

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The syntheses and molecular structures, as determined by single-crystal X-ray diffraction analysis, of the first intramolecularly [4ϩ2]-coordinated tetraorganolead compound {4-t-Bu-2,6-[P(O)(OEt) 2 ] 2 C 6 H 2 }PbPh 3 (2) and the triphenyllead chloride adduct of the first intramolecularly coordinated benzoxaphosphaplumbole {[1(Pb),3(P)-Pb(Ph) 2 OP(O)(OEt)-5-t-Bu-7-P(O)-(OEt) 2 ]C 6 H 2 ·Ph 3 PbCl} (3a) are reported. The reaction of 2 with [Ph 3 C] ϩ [PF 6 ] Ϫ and p-MeC 6 H 4 SO 3 H, respectively, provides the

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Metallorganische Pinzetten-Komplexe von Elementen der Platingruppe: Sensoren, Schalter und Katalysatoren

2001

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Seit den ersten Berichten über Übergangsmetallkomplexe mit Pinzetten‐Liganden in den späten siebziger Jahren haben diese Systeme wegen der ungewöhnlichen Eigenschaften, die das Metallzentrum durch den Pinzetten‐Liganden erhält, zunehmendes Interesse hervorgerufen. Typischerweise enthält ein solcher Ligand einen anionischen Arenring, der an beiden ortho‐Positionen mit Heteroatomsubstituenten, z. B. CH2NR2, CH2PR2 oder CH2SR, substituiert ist. Die Heteroatomsubstituenten koordinieren im Allgemeinen ebenfalls an das Metallzentrum und unterstützen daher die M‐C‐σ‐Bindung. Häufig führt dies zu einer dreizähnigen meridionalen Koordination, bei der zwei Metallacyclen gebildet werden, die sich die M‐C‐Bindung teilen. Detaillierte Studien zur Bildung und zu den Eigenschaften einer großen Vielfalt an Pinzetten‐Komplexen von Elementen der Platingruppe führten sowohl zu einem grundlegenden Verständnis vieler Reaktionen der Organometallchemie als auch zu einer Reihe neuer Anwendungen. Die Entdeckung von Katalysatoren für die Alkandehydrierung, die Aufklärung der Mechanismen bestimmter Basisreaktionen (z. B. der C‐C‐Aktivierung) sowie die Entwicklung der ersten wiederverwendbaren Metallodendrimere als Katalysatoren in der homogenen Katalyse und kristalliner Schalter zur Materialveredelung sind nur einige der vielen Höhepunkte, die aus den vielfältigen Untersuchungen hervorgegangen sind. In dieser Übersicht werden zum einen die Synthesemethoden besprochen, die zurzeit für die Herstellung von Komplexen aus Elementen der Platingruppe und Pinzetten‐Liganden bekannt sind. Zum anderen werden vor allem Anwendungen von Pinzetten‐Komplexen in den Materialwissenschaften, wie die Entwicklung und Veredelung von Sensoren, Schaltern und Katalysatoren, diskutiert.

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Cited by 78 publications

References 8 publications

Substituted 4,4′-Stilbenoid NCN-Pincer Platinum(II) Complexes. Luminescence and Tuning of the Electronic and NLO Properties and the Application in an OLED

Substituted 4,4′-Stilbenoid NCN-Pincer Platinum(II) Complexes. Luminescence and Tuning of the Electronic and NLO Properties and the Application in an OLED

The First [4+2]-Coordinated Tetraorganolead Compound: Synthesis, Structure and Conversion into a Triorganolead Cation, a Benzoxaphosphaplumbole, and Diorganolead Dihalides

Metallorganische Pinzetten-Komplexe von Elementen der Platingruppe: Sensoren, Schalter und Katalysatoren

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