Fluorine in Cyclometalated Platinum Compounds

Crespo, Margarita

doi:10.1021/om200835g

Cited by 58 publications

(34 citation statements)

References 121 publications

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“…24 Among reactions of aliphatic hydrofluorocarbons in solution, we draw attention to the reactions of CH 3 F and CHF 3 at iridium pincer complexes 42 and the discovery of niobium complexes that are selective for activation of benzylic CF 3 groups, even in the presence of C-H bonds. 43 Carbon-fluorine bond activation has been the subject of numerous recent reviews, [33][34][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] but competing C-H bond activation receives little attention in most of these publications. Two reviews pay particular attention to partially fluorinated substrates and C-H activation, one on nickel chemistry 62 and the other on organometallic chemistry particularly with fluorobenzene and difluorobenzene.…”

Section: Scheme 1 Coordination Of Hydrofluoroarenes and Hydrofluoroamentioning

confidence: 99%

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

2017

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Partially fluorinated alkanes, arenes, and alkenes can be transformed by a variety of transition metal and lanthanide systems. Although the C-H bond is weaker than the C-F bond regardless of the hybridization of the carbon, the reaction of the C-F bond at the metal is usually more exothermic than the corresponding reaction of the C-H bonds. Both bonds are activated by the metal systems, but the preference for activating these bonds depends on the nature of the hydrocarbon and of the metal system, so that the reaction can be directed exclusively toward C-H or C-F bonds or yield a mixture of products. Additionally, the presence of fluorine differentiates between C-H bonds at different positions resulting in regioselective C-H bond activation; paradoxically, the strongest C-H bond reacts preferentially. The purpose of this review is to describe the field of reactions of partially fluorinated substrates with transition metal atoms, ions, and molecular complexes. The controlling physical properties (thermodynamics and kinetics) are described first, followed by a description of stoichiometric reactions, with the competition between the C-H and C-F activations as focus. A few representative catalytic systems are discussed. The review also highlights the benefit of combining experimental and theoretical studies.

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Section: Scheme 1 Coordination Of Hydrofluoroarenes and Hydrofluoroamentioning

confidence: 99%

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

2017

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“…23,[28][29][30] The good electroluminescence behaviors of trifluoromethyl-substituted complexes may provide great opportunities to improve their applications in oxygen sensing. Relative to Ir(ppy) 2 (acac) (F p = 0.34), these Ir(III) complexes show high quantum efficiencies (F p ), which are probably attributed to the C-F bond of the ligand that can reduce the undesirable nonradioactive pathways.…”

Section: Photophysical and Thermal Propertiesmentioning

confidence: 99%

Trifluoromethyl-substituted cyclometalated iridium^III emitters with high photostability for continuous oxygen sensing

Xing

et al. 2015

J. Mater. Chem. C

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Trifluoromethyl-substituted cyclometalated Ir(III) complexes have been prepared and fully characterized.The photophysical and electrochemical properties of the complexes were investigated systematically. All iridium complexes exhibit high photoluminescence quantum yields, high oxidation potentials and good photostability against continuous irradiation. The optimum loading level of the Ir(III) complexes incorporated into oxygen-sensitive films has been discussed. Three different polymers were investigated for the development of efficient oxygen-sensitive films. All Ir(III) complexes immobilized in ethyl cellulose demonstrated quick responses to various oxygen concentrations and high sensitivity upon changes of oxygen partial pressure. These cyclometalated Ir(III) complexes with high photostability are potential candidates for online continuous monitoring of oxygen concentrations. ; Tel: +86-411-84986182 † Electronic supplementary information (ESI) available: Materials and methods, characterization of ligands, thermogravimetric analysis, and cyclic voltammograms. See

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“…Π‐extended cyclometalating ligands would be expected to offer the metal ion, a strong ligand field and consequently produce significant changes in the physical and chemical properties . In particular, cyclometalated platinum complexes have attracted long‐lasting interest due to their potential applications in a wide range of research areas such as organometallic synthesis, catalysis, organic light‐emitting diode (OLED) and the design of antitumor agents . The C^N‐cycloplatinated (II) complexes, where C^N = chelating carbon‐nitrogen donor ligand, were found to be reactive substrates for oxidative addition reactions …”

Section: Introductionmentioning

confidence: 99%

Carbon‐iodide bond activation by cyclometalated Pt (II) complexes bearing tricyclohexylphosphine ligand: A comparative kinetic study and theoretical elucidation

Chamyani

Shahsavari

Abedanzadeh

et al. 2018

Applied Organom Chemis

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Yield: 76%. Elem. anal. Calcd for C 30 H 44 NPPt (644.73); C, 55.89; H, 6.88; N, 2.17. Found: C, 55.76; H, 6.82; N, 2.26. 1 H NMR (400 MHz, CDCl 3 ): δ = 1.07 (d, 3 J PH = 5.3 Hz, 2 J PtH = 84.5 Hz, 3H, PtMe), 1.20-1.40 (m, 9H, Cy), 1.65 (m, 6H, Cy), 1.70-1.90 (m, 9H, Cy), 1.97-2.14 (m, 6H, Cy), 2.36 (m, 3H, Cy), 7.09 (m, 1H, H 4′ ), 7.16 (t, 1H, 3 J HH = 7.3 Hz, H 5′ ), 7.35 (td, 1H, 3 J HH = 7.3 Hz, 4 J HH = 2.9 Hz, 4 J PtH = 29.7 Hz, H 5 ), 7.70 (bd, 1H, 3 J HH = 7.8, H 4 ), 7.85 (m, 2H, H 3 and H 6′ ), 7.95 (dd, 1H, 3 J HH = 6.3 Hz, 4 J HH = 1.1 Hz, 3 J PtH = 46.8 Hz, H 3′ ), 8.84 (d, 1H, 3 J HH = 5.6 Hz, 3 J PtH = 18.3 Hz, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −15.3 (d, 2 Yield: 81%. Elem. anal. Calcd for C 32 H 44 NPPt (668.75); C, 57.47; H, 6.63; N, 2.09. Found: C, 57.31; H, 6.69; N, 2.21. 1 H NMR (400 MHz, CDCl 3 ): δ = 0.83-2.61 (3H of Me and 33H of Cy), 7.46 (dd, 1H, 3 J HH = 7.9 Hz, 3 J HH = 7.8 Hz, H 8 ), 7.56 (d, 1H, 3 J HH = 8.1 Hz, H 6 ), 7.67 (d, 1H, 3 J HH = 8.1 Hz, H 5 ), 7.74 (m, 1H, H 3 ), 7.82 (d, 1H, 3 J HH = 8.7 Hz, H 7 ), 8.23 (dd, 1H, 3 J HH = 7.1 Hz, 3 J PtH = 45.5 Hz, H 9 ), 8.34 (d, 1H, 3 J HH = 8.3 Hz, H 4 ), 9.15 (d, 1H, 3 J HH = 5.3 Hz, 4 J HH = 1.1 Hz, 3 J PtH = 17.2 Hz, H 2 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −16.0 (d, 2 J PC = 7 Hz, 1 J PtC = 754 Hz, PtMe), 26.6 (s, C of PCy 3 ), 1 H NMR (400 MHz) in CDCl 3 : δ = 0.86-2.11 (39H, aliphatic region, overlapping multiplets of 2Me and 3Cy), 7.21 (m, 1H, 3 J HH = 6.6 Hz, H 4′ ), 7.50 (dd, 2H, 3 J HH = 6.5 Hz, 4 J HH = 2.1 Hz, 4 J PtH = 53.1 Hz, H 5 and H 3′ ), 8.03 (m, 1H, 3 J HH = 7.9 Hz, 3 J HH = 7.8 Hz, H 4 ), 8.22 (d, 1H, 3 J HH = 6.5 Hz, H 5′ ), 10.09 (d, 3 J HH = 5.5 Hz, 4 J PtH = 16.1 Hz, 1H, H 3 ), 10.26 (d, 1H, 3 J HH = 7.83 Hz, 1H, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −7.3 (d, 2 J PC = 4 Hz, 1 J PtC = 624 Hz, PtMe (Me trans to N)), 10.7 (d, 2 J PC = 106 Hz, 1 J PtC = 461 Hz, PtMe (Me trans J PtP = 955 Hz, 1P of PCy 3 ); 195 Pt{ 1 H} NMR (86 MHz, CDCl 3 ): δ = −3215.1 (s, 1 J PtP = 957 Hz, 1Pt). 4.3.2 | cis-[PtMe 2 I(k 2 N,C-ppy)(PCy 3 )] (2a) 1 H NMR (400 MHz) in CDCl 3 : δ = 0.85-2.12 (39H, aliphatic region, overlapping multiplets of 2Me and 3Cy), 7.22 (dd, 3 J HH = 7.8 Hz, 3 J HH = 7.3 Hz, 1H, H 4′ ), 7.33 (m, 2H, H 5′ and H 6′ ), 7.50 (d, 2H, 3 J HH = 7.8 Hz, 4 J PtH = 48.9 Hz, H 3′ ), 7.71 (m, 1H, H 4 ), 7.87 (ddd, 3 J HH = 7.5 Hz, 3 J HH = 8.0 Hz, 4 J HH = 1.3 Hz, 1H, H 5 ), 7.96 (d, 1H, 3 J HH = 8.1 Hz, H 3 ), 10.12 (d, 1H, 3 J HH = 14.8 Hz, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −7.3 (d, 2 J PC = 3 Hz, 1 J PtC = 670 Hz, PtMe (Me trans to N)), 10.4 (d, 2 J PC = 109 Hz, 1 J PtC = 469 Hz, PtMe (Me trans to P)), 26.4 (s, C of PCy 3 ), 27.9 (d, 3 J PC = 10 Hz, C of

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Fluorine in Cyclometalated Platinum Compounds

Abstract: This article is focused on the chemistry of cyclometalated platinum compounds containing fluorine.

Cited by 58 publications

References 121 publications

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

Trifluoromethyl-substituted cyclometalated iridium^III emitters with high photostability for continuous oxygen sensing

Carbon‐iodide bond activation by cyclometalated Pt (II) complexes bearing tricyclohexylphosphine ligand: A comparative kinetic study and theoretical elucidation

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Fluorine in Cyclometalated Platinum Compounds

Abstract: This article is focused on the chemistry of cyclometalated platinum compounds containing fluorine.

Cited by 58 publications

References 121 publications

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

Trifluoromethyl-substituted cyclometalated iridiumIII emitters with high photostability for continuous oxygen sensing

Carbon‐iodide bond activation by cyclometalated Pt (II) complexes bearing tricyclohexylphosphine ligand: A comparative kinetic study and theoretical elucidation

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Trifluoromethyl-substituted cyclometalated iridium^III emitters with high photostability for continuous oxygen sensing