Supramolecular Polymer and Sheet and a Double Cubane Structure in Platinum(IV) Iodide Chemistry: Solution of a Longstanding Puzzle

Fard, Mahmood Azizpoor; Behnia, Ava; Puddephatt, Richard J.

doi:10.1021/acsomega.8b01367

Cited by 11 publications

(8 citation statements)

References 36 publications

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“…A doublet with Pt satellites at δ = 31.6 was assigned to the C atom of CH 2 in the benzyl group, which was further confirmed by DEPT 13 C NMR analysis (see Figure ). The coupling constants mentioned above are typical values for Pt(IV) complexes. ,− …”

Section: Results and Discussionmentioning

confidence: 99%

Ligand-Mediated C–Br Oxidative Addition to Cycloplatinated(II) Complexes and Benzyl-Me C–C Bond Reductive Elimination from a Cycloplatinated(IV) Complex

et al. 2020

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Reaction of the Pt(II) complexes [PtMe2(pbt)], 1a, (pbt = 2-(2-pyridyl)benzothiazole) and [PtMe(C^N)(PPh2Me)] [C^N = deprotonated 2-phenylpyridine (ppy), 1b, or deprotonated benzo[h]quinoline (bhq), 1c] with benzyl bromide, PhCH2Br, is studied. The reaction of 1a with PhCH2Br gave the Pt(IV) product complex [PtBr(CH2Ph)Me2(pbt)]. The major trans isomer is formed in a trans oxidative addition (2a), while the minor cis products (2a′ and 2a″) resulted from an isomerization process. A solution of Pt(II) complex 1a in the presence of benzyl bromide in toluene at 70 °C after 7 days gradually gave the dibromo Pt(IV) complex [Pt(Br)2Me2(pbt)], 4a, as determined by NMR spectroscopy and single-crystal XRD. The reaction of complexes 1b and 1c with PhCH2Br gave the Pt(IV) complexes [PtMeBr(CH2Ph)(C^N)(PPh2Me)] (C^N = ppy; 2b; C^N = bhq, 2c), in which the phosphine and benzyl ligands are trans. Multinuclear NMR spectroscopy ruled out other isomers. Attempts to grow crystals of the cycloplatinated(IV) complex 2b yielded a previously reported Pt(II) complex [PtBr(ppy)(PPh2Me)], 3b, presumably from reductive elimination of ethylbenzene. UV–vis spectroscopy was used to study the kinetics of reaction of Pt(II) complexes 1a–1c with benzyl bromide. The data are consistent with a second-order SN2 mechanism and the first order in both the Pt complex and PhCH2Br. The rate of reaction decreases along the series 1a ≫ 1c > 1b. Density functional theory calculations were carried out to support experimental findings and understand the formation of isomers.

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Section: Results and Discussionmentioning

confidence: 99%

Ligand-Mediated C–Br Oxidative Addition to Cycloplatinated(II) Complexes and Benzyl-Me C–C Bond Reductive Elimination from a Cycloplatinated(IV) Complex

et al. 2020

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“…The aminopyridine ligands L1–L3 , which contain phenol substituents at the amine donor, and their dimethylplatinum(II) complexes, which have been reported earlier, are shown in Scheme . , The complexes [PtMe 2 ( L )], 3 – 5 , are difficult to isolate from the equilibrium mixture formed by reaction between [Pt 2 Me 4 (μ-SMe 2 ) 2 ], 1 , and the ligands L1–L3 (Scheme ), and subsequent reactions were carried out from the complexes formed in situ …”

Section: Resultsmentioning

confidence: 99%

“…11,12 The complexes [PtMe 2 (L)], 3−5, are difficult to isolate from the equilibrium mixture formed by reaction between [Pt 2 Me 4 (μ-SMe 2 ) 2 ], 1, 13 and the ligands L1−L3 (Scheme 2), and subsequent reactions were carried out from the complexes formed in situ. 12 Oxidative Addition Chemistry of Complexes 3−5. Complexes 4 and 5 were stable in solutions in acetone, but complex 3 was less stable (see below).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The NMR labeling is shown in Chart . The complex [Pt 2 Me 4 (μ-SMe 2 ) 2 ], dimethylplatinum(II) complexes 3–5 , and ligands L1–L4 were synthesized according to literature procedures. ,,, …”

Section: Methodsmentioning

confidence: 99%

“…The complex [Pt 2 Me 4 (μ-SMe 2 ) 2 ], dimethylplatinum(II) complexes 3−5, and ligands L1−L4 were synthesized according to literature procedures. 12,13,19,20 Structure Determinations. 21 Single-crystal X-ray diffraction measurements were made using a Bruker APEX-II charge coupled device diffractometer with graphite-monochromated Mo Kα (λ = 0.71073 Å) radiation.…”

Section: ■ Conclusionmentioning

confidence: 99%

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Models for Cooperative Catalysis: Oxidative Addition Reactions of Dimethylplatinum(II) Complexes with Ligands Having Both NH and OH Functionality

2019

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The role of NH and OH groups in the oxidative addition reactions of the complexes [PtMe 2 (κ 2 - N , N ′- L )], L = 2-C 5 H 4 NCH 2 NH- x -C 6 H 4 OH [ 3 , x = 2, L = L1 ; 4 , x = 3, L = L2 ; 5 , x = 4, L = L3 ], has been investigated. Complex 3 is the most reactive. It reacts with CH 2 Cl 2 to give a mixture of isomers of [PtMe 2 (CH 2 Cl)(κ 3 - N , N ′, O -( L1 -H)], 6 , and decomposes in acetone to give [PtMe 3 (κ 3 - N , N ′, O -( L1 -H)], 7 , both of which contain the fac tridentate deprotonated ligand. Complex 3 reacts with MeI to give complex 7 , whereas 4 and 5 react to give [PtIMe 3 (κ 2 - N , N ′- L2 ))], 8 , or [PtIMe 3 (κ 2 - N , N ′- L3 )], 9 , respectively. Each complex 3 , 4 , or 5 reacts with either dioxygen or hydrogen peroxide to give the corresponding complex [Pt(OH) 2 Me 2 (κ 2 - N , N ′- L )], 10 , L = L1 ; 11 , L = L2 ; 12 , L = L3 . The ligand L3 in complexes 9 and 12 is easily oxidized to the corresponding imine ligand 2-C 5 H 4 NCH=N-4-C 6 H 4 OH, L4 , in forming the complexes [PtIMe 3 (κ 2 - N , N ...

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Complexes Containing a Phenol–Platinum(II) Hydrogen Bond: Synthons for Supramolecular Self‐Assembly and Precursors for Hydridoplatinum(IV) Complexes

et al. 2019

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The cycloneophylplatinum(II) complexes [Pt(CH2CMe2C6H4)(κ2‐NN′‐2‐C5H4NCH2‐NH‐R], R = 2‐C6H4OH, 1; R = 3‐C6H4OH, 2; R = 4‐C6H4OH, 3, and [Pt(CH2CMe2C6H4)(κ2‐NN′‐2‐C5H4NCH=N‐2‐C6H4OH)], 4, are reported. The structures of 1 and 4 each contain an intramolecular OH··Pt hydrogen bond, while complex 3 contains an intermolecular OH··Pt hydrogen bond and forms a new type of supramolecular polymer. In contrast, the complex [PtCl2(κ2‐NN′‐2‐C5H4NCH=N‐2‐C6H4OH)], 5, forms a dimer through intermolecular OH··ClPt hydrogen bonding. Reaction of complex 4 with HCl or HBr occurs by oxidative addition to give hydridoplatinum(IV) complexes [PtHX(CH2CMe2C6H4)(κ2‐NN′‐2‐C5H4NCH=N‐2‐C6H4OH)], 6, X = Cl; 7, X = Br. The sequential formation of isomers of these compounds is interpreted in terms of a proposed reaction mechanism.

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Supramolecular Polymer and Sheet and a Double Cubane Structure in Platinum(IV) Iodide Chemistry: Solution of a Longstanding Puzzle

Abstract: The complexes [PtMe 2 ( L )], L = 2-C 5 H 4 NCH 2 NH- x -C 6 H 4 OH ( x = 2, 3, or 4), react with iodine to form [PtI 2 Me 2 ( L )], by trans oxidative addition, when x = 3 or 4, and they are s… Show more

Cited by 11 publications

References 36 publications

Ligand-Mediated C–Br Oxidative Addition to Cycloplatinated(II) Complexes and Benzyl-Me C–C Bond Reductive Elimination from a Cycloplatinated(IV) Complex

Ligand-Mediated C–Br Oxidative Addition to Cycloplatinated(II) Complexes and Benzyl-Me C–C Bond Reductive Elimination from a Cycloplatinated(IV) Complex

Models for Cooperative Catalysis: Oxidative Addition Reactions of Dimethylplatinum(II) Complexes with Ligands Having Both NH and OH Functionality

Complexes Containing a Phenol–Platinum(II) Hydrogen Bond: Synthons for Supramolecular Self‐Assembly and Precursors for Hydridoplatinum(IV) Complexes

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