Photophysical properties of a series of cycloplatinated(<scp>ii</scp>) complexes featuring allyldiphenylphosphane

Shahsavari, Hamid R.; Aghakhanpour, Reza Babadi; Babaghasabha, Mojgan; Haghighi, Mohsen Golbon; Nabavizadeh, S. Masoud; Notash, Behrouz

doi:10.1039/c7nj00055c

Cited by 27 publications

(41 citation statements)

References 63 publications

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“…The coupling constants of 1 J PtP = 2162 Hz ( 1 ), 1937 Hz ( 2 ) and 2052 Hz ( 3 ) are typical for the P‐ trans ‐C (sp 2 ) geometry . It is noteworthy that this significant difference in the coupling values of 1 J PtP (about 120 Hz), is attributed to the trans influence of coordinated carbon atom of the C^N‐cyclometalated ligands (Obpy > bzq > ppy) . The 195 Pt{ 1 H} NMR spectra of these complexes contain a doublet resonance with a coupling constant value that is almost equal to that observed in the corresponding 31 P{ 1 H} NMR spectra.…”

Section: Resultsmentioning

confidence: 94%

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: Resultsmentioning

confidence: 94%

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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“…As depicted by perspective ORTEP view of the structures (Figure ), the allyl substituents of the PPh 2 allyl phosphane ligands are obviously detected to be perpendicular to the molecule plane in each structure. The distances between Pt(II) and the PPh 2 allyl moieties (Pt1‐P1=2.241(2) Å and Pt1‐P2=2.238(3) Å) in A , (Pt1A‐P1A=2.2980(4) Å and Pt1B‐P1B 2.3129(4) Å) in 1 a , or (Pt1‐P1=2.3015(6) Å) in 1 b and (Pt1‐P1=2.3031(5) Å) in 1 c , are in the same range as those found in similar Pt(II)‐phosphane complexes . The distances of the Pt−S bonds are almost equal in 1 a – c (∼2.33 Å).…”

Section: Resultsmentioning

confidence: 99%

“…The distances between Pt(II) and the PPh 2 allyl moieties (Pt1-P1 = 2.241(2) Å and Pt1-P2 = 2.238(3) Å) in A, (Pt1A-P1A = 2.2980(4) Å and Pt1B-P1B 2.3129(4) Å) in 1 a, or (Pt1-P1 = 2.3015(6) Å) in 1 b and (Pt1-P1 = 2.3031(5) Å) in 1 c, are in the same range as those found in similar Pt(II)-phosphane complexes. [23] The distances of the PtÀ S bonds are almost equal in 1 a-c (~2.33 Å). It is notable that the pyridyl moiety in the k 1 -S-SR ligand is approximately perpendicular to the metal plane.…”

Section: Synthesis and Characterizationmentioning

confidence: 98%

trans‐Platinum(II) Thionate Complexes: Synthesis, Structural Characterization, and in vitro Biological Assessment as Potent Anticancer Agents

et al. 2019

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A series of Pt(II) complexes trans‐[Pt(PPh2allyl)2(κ1‐S‐SR)2], 1, PPh2allyl=allyldiphenylphosphine, SR=pyridine‐2‐thiol (Spy, 1 a), 5‐(trifluoromethyl)‐pyridine‐2‐thiol (SpyCF3‐5, 1 b), pyrimidine‐2‐thiol (SpyN, 1 c), benzothiazole‐2‐thiol (Sbt, 1 d), benzimidazole‐2‐thiol (Sbi, 1 e), were synthesized. They were characterized by NMR, HR ESI‐MS, and X‐ray crystallography. Treatment of human cancer cell lines (A549, SKOV3, MCF‐7) with these complexes resulted in promising antitumor effects in comparison with cisplatin. These compounds showed suitable selectivity between tumorigenic and non‐tumorigenic (MCF‐10 A) cell lines. Analyses of cell cycle progression and apoptosis were conducted for 1 a, the most cytotoxic compound, to screen dose/time response and to study the antiproliferative mechanism. An electrophoresis mobility shift assay was performed to assess the direct interaction of 1 a with DNA and the strong genotoxic ability was indicated through the comet assay method.

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“…Another discrete signal assignable to the H 3 proton of O‐bpy appears as a sharp doublet signal. This signal is considerably deshielded to near 10 ppm due to being directly in contact through space with oxygen atom of the O‐bpy …”

Section: Resultsmentioning

confidence: 99%

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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Photophysical properties of a series of cycloplatinated(ii) complexes featuring allyldiphenylphosphane

Abstract: Cycloplatinated(ii) complexes 1–4 were synthesized and characterized. All complexes exhibit strong luminescence except 3.

Cited by 27 publications

References 63 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

trans‐Platinum(II) Thionate Complexes: Synthesis, Structural Characterization, and in vitro Biological Assessment as Potent Anticancer Agents

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

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