Reactivity comparison of five-and six-membered cyclometalated platinum(<scp>ii</scp>) complexes in oxidative addition reactions

Raoof, Fatemeh; Boostanizadeh, Maryam; Esmaeilbeig, Ahmad R.; Nabavizadeh, S. Masoud; Aghakhanpour, Reza Babadi; Ghiassi, Kamran B.; Olmstead, Marilyn M.; Balch, Alan L.

doi:10.1039/c5ra17421j

Cited by 24 publications

(12 citation statements)

References 31 publications

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“…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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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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“…Interestingly, there are many reports in the literature that theoretical calculations support the experimental kinetic data . In the previous investigations, particularly for the reported cycloplatinated(II) complexes, it has been proven that the roles of cyclometalated and ancillary ligands are very important in determining the reaction rate . For example, the ancillary monophosphanes, containing a wide range of substituents, are the appropriate choices for tuning the oxidative addition reaction rate of cycloplatinated(II) complexes due to their various electronic and steric effects …”

Section: Introductionmentioning

confidence: 86%

Stable trans isomer as the kinetic and theromodynamic product for the oxidative addition of MeI to cycloplatinated(II) complexes comprising isocyanide ligands

Shahsavari

Aghakhanpour

Hossein-Abadi

et al. 2018

Applied Organom Chemis

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The present investigation introduces a new series of cycloplatinated(II) complexes, with the general formula Pt(O-bpy)(Me)(CN-R)] (R = benzyl, 2-naphtyl and tert-butyl), which are able to generate the stable trans-Pt(IV) product in the solution after the reaction with iodomethane. In fact, the trans product is both the kinetic and thermodynamic product of the reaction; this observation was supported by DFT calculations. These Pt(II) complexes are supported by 2,2'-bipyridine N-oxide (O-bpy) and one of several isocyanides as the cyclometalated and ancillary ligands, respectively. These new Pt(II) complexes undergo oxidative addition with MeI to give the corresponding trans-Pt(IV) complexes. All the complexes were identified employing the multi-nuclear NMR spectroscopy and single crystal X-ray crystallography. The kinetic investigations were also performed for the oxidative addition reactions in order to measure the reaction rates; the reaction was followed by UV-Vis spectroscopy. The rates obtained follow the trend CN-t Bu > CN-Bz > CN-2 Np for the CN-R ligands in the Pt(II) complexes. The order can be related to the degree of electron-donation of the R group (tert-butyl > benzyl > 2-naphtyl).

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“…5 The precursor complex, [Pt(Me) 2 (DMSO) 2 ], A, was prepared by the literature method. [53] Bis(diphenylphosphino)acetylene (dppac), 2-(2pyridyl) benzimidazole (Hpbz), PPh 2 Me and PPh 3 were purchased from commercial sources. The 1 H NMR labeling for the pbz ligand is shown in Chart 1 for clarifying the chemical shift assignments.…”

Section: General Remarksinstruments and Techniquesmentioning

confidence: 99%

Synthesis, structural characterization, and luminescence properties of mono- and di-nuclear platinum(II) complexes containing 2-(2-pyridyl)-benzimidazole

Niknam

Hamidizadeh

Nabavizadeh

et al. 2019

Inorganica Chimica Acta

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The starting complex [Pt(Me)(DMSO)(pbz)], (1, (pbz = 2-(2pyridyl)benzimidazolate) was prepared by a known method using the 1 reaction of [Pt(Me) 2 (DMSO) 2 ], A, with Hpbz at room temperature. Reaction of 1 with an equivalent of a phosphine ligand gave the neutral mononuclear complexes [Pt(Me)(L)(pbz)], )] ( 2, (L = PPh 3 ) or and 3, (L =PPh 2 Me). Reaction of 1 with 0.5 equivalent of the linear diphosphine 1,1'-bis(diphenylphosphino)acetylene (dppac) gave the binuclear complex [Pt 2 (Me) 2 (μ-dppac)(pbz) 2 ], 4. All Each the complexes were was fully characterized by NMR spectroscopy, X-ray crystallography and mass spectrometry. The photophysical properties of the complexes were investigated in under different conditions and interpretation was, supported by TD-DFT calculations. The low-lying transitions in the absorption and emission spectra were assigned as having LLCT/MLCT (ligand to ligand charge transfer/metal-to-ligand charge transfer) character. We also describe the luminescence properties of [Pt(Me)(PPh 3 ) (ppy)], 7, and [Pt(Me)(PPh 2 Me)(ppy)], 8, (ppy is 2-phenylpyridinate), the (N^C  ) analogues of 2 and 3.

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Reactivity comparison of five-and six-membered cyclometalated platinum(ii) complexes in oxidative addition reactions

Cited by 24 publications

References 31 publications

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

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

Stable trans isomer as the kinetic and theromodynamic product for the oxidative addition of MeI to cycloplatinated(II) complexes comprising isocyanide ligands

Synthesis, structural characterization, and luminescence properties of mono- and di-nuclear platinum(II) complexes containing 2-(2-pyridyl)-benzimidazole

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