Reactivity of a new aryl cycloplatinated(<scp>ii</scp>) complex containing rollover 2,2′-bipyridine <i>N</i>-oxide toward a series of diphosphine ligands

Shahsavari, Hamid R.; Aghakhanpour, Reza Babadi; Hossein-Abadi, Mojdeh; Kia, Reza; Halvagar, Mohammad Reza; Raithby, Paul R.

doi:10.1039/c8nj00713f

Cited by 10 publications

(12 citation statements)

References 51 publications

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“…As shown in Figure , Pt (IV) center adopts a slightly distorted octahedral environment, surrounded by carbon‐nitrogen donor atoms of the Obpy ligand (C1, N2), a carbon atom of Me ligand (Cl2) and an iodine atom (I1) while the other Me group (Cl1) besides the PCy 3 moiety (P1) situated in the axial positions. The dihedral angle between the aromatic rings of the cyclometalated Obpy ligand is 7.4° which is in good agreement with previous reports …”

Section: Resultssupporting

confidence: 93%

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: Resultssupporting

confidence: 93%

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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“…Some mono- and dinuclear complexes with diphosphines have been reported earlier in this review. Other series of mono, and dinuclear complexes with diphosphines, 45 – 48 (see Figure 32 ), have been reported by us [ 76 ] and other researchers [ 77 , 78 ], comprising the bipyridine N -Oxide complex [Pt(N^C)(dppm)(p-tolyl)], 49 , analogous to 48 , with p-tolyl in place on methyl.…”

Section: C–h Bond Activation Through Rollover Cyclometalationmentioning

confidence: 68%

Rollover Cyclometalation as a Valuable Tool for Regioselective C–H Bond Activation and Functionalization

Zucca

Pilo

2021

Molecules

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Rollover cyclometalation constitutes a particular case of cyclometallation reaction. This reaction occurs when a chelated heterocyclic ligand loses its bidentate coordination mode and undergoes an internal rotation, after which a remote C–H bond is regioselectively activated, affording an uncommon cyclometalated complex, called “rollover cyclometalated complex”. The key of the process is the internal rotation of the ligand, which occurs before the C–H bond activation and releases from coordination a donor atom. The new “rollover” ligand has peculiar properties, being a ligand with multiple personalities, no more a spectator in the reactivity of the complex. The main reason of this peculiarity is the presence of an uncoordinated donor atom (the one initially involved in the chelation), able to promote a series of reactions not available for classic cyclometalated complexes. The rollover reaction is highly regioselective, because the activated C–H bond is usually in a symmetric position with respect to the donor atom which detaches from the metal stating the rollover process. Due to this novel behavior, a series of potential applications have appeared in the literature, in fields such as catalysis, organic synthesis, and advanced materials.

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“…The appropriate single crystals were grown by slow diffusion of n -hexane into a CH 2 Cl 2 solution of 2a at ambient temperature under air. A slightly distorted octahedral geometry is observed about the Pt metal center, and the main deviation from ideal angle is referred to the angle of Obpy ligand (C(10)–Pt–(1)N(1) = 80.077(3)°), which is comparable to the corresponding angle in the other reported cycloplatinated(II/IV) structures. ,, The two acetate groups are mutually trans in the octahedral structure. Moreover, it is worth mentioning that the Pt–C, Pt–N, and Pt–O bond lengths are close to the other Pt(IV) structures which have already been reported.…”

Section: Resultsmentioning

confidence: 99%

Oxidative Addition of a Hypervalent Iodine Compound to Cycloplatinated(II) Complexes for the C–O Bond Construction: Effect of Cyclometalated Ligands

et al. 2021

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The complex [PtMe(Obpy)(OAc)2(H2O)], 2a, Obpy = 2,2′-bipyridine N-oxide, is prepared through the reaction of [PtMe(Obpy)(SMe2)], 1a, by 1 equiv of PhI(OAc)2 via an oxidative addition (OA) reaction. Pt(IV) complex 2a attends the process of C–O bond reductive elimination (RE) reaction to form methyl acetate and corresponding Pt(II) complex [Pt(Obpy)(OAc)(H2O)], 3a. The kinetic of OA and RE reactions are investigated by means of different spectroscopies. The obtained results show that the reaction rates of OA step of 1a are faster than its analogous complex [PtMe(ppy)(SMe2)], 1b, ppy = 2-phenylpyridine. The density functional theory (DFT) calculations signify that the OA reaction initiated by a nucleophilic attack of the platinum(II) central atom of 1b on the iodine(III) atom while it had commenced by a nucleophilic substitution reaction of coordinated SMe2 in 1a with a carbonyl oxygen atom of PhI(OAc)2. Our calculation revealed that the key step for 1a is an acetate transfer from the I(III) to Pt(II) through a formation of square pyramidal iodonium complex. This can be attributed to the more electron-withdrawing character of Obpy ligand than to ppy which reduces the nucleophilicity of Pt atom in 1a. Furthermore, 2a with electron-withdrawing Obpy ligand prone to C–O bond formation faster than complex [PtMe(ppy)(OAc)2(H2O)], 2b, with an electron-rich ppy ligand which conforms to the anticipation that REs occur faster on electron-poor metal centers.

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Reactivity of a new aryl cycloplatinated(ii) complex containing rollover 2,2′-bipyridine N-oxide toward a series of diphosphine ligands

Abstract: A new rollover cycloplatinated(ii) complex was prepared. The reactivity of this complex was investigated towards a wide range of diphosphine ligands.

Cited by 10 publications

References 51 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

Rollover Cyclometalation as a Valuable Tool for Regioselective C–H Bond Activation and Functionalization

Oxidative Addition of a Hypervalent Iodine Compound to Cycloplatinated(II) Complexes for the C–O Bond Construction: Effect of Cyclometalated Ligands

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