Biscyclometalated platinum complexes with thiophene ligands

Anderson, Craig M.; Weinstein, Michael A.; Morris, James; Kfoury, Nicole; Duman, Leila M.; Balema, Tedros A.; Kreider-Mueller, Ava; Scheetz, Perry M.; Ferrara, Skylar J.; Chierchia, Matteo; Tanski, Joseph M.

doi:10.1016/j.jorganchem.2012.10.027

Cited by 17 publications

(18 citation statements)

References 67 publications

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“…Similar values for these coupling constants were observed for the platinum products of L2. The magnitude of these coupling constants is diagnostic of a Pt(II) oxidation state in our complexes, and these values compare favorably to those found in recent publications [41,49,[58][59][60][61]. While these spectroscopic features of the proton NMR spectra allow us to conclude that we are observing two different Pt(II) complexes, the identity of the five vs. seven membered product as major or minor isomer was determined by relative integration of the different peaks in the upfield methyl/methylene region to the imine resonance in the NMR spectrum.…”

Section: Reactions Of Ligands L1 and L2 With Cis-[pt2me4(µ-sme2)2 Ptasupporting

confidence: 90%

“…The iodide is trans to the strong sigma donor carbon ligand. The angles and bonds lengths about the metal center are in the accepted range for platinum(II) cyclometalated complexes [49]. The pucker in the seven-membered ring is observed with the methylene angle of Pt-C(1)-C(2) = 99.8(1)º, clearly indicating sp 3 hybridization, but being strained to some degree.…”

Section: Reactions Of Ligands L1 and L2 With Cis-[pt2me4(µ-sme2)2 Ptamentioning

confidence: 78%

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Regioselective competition between the formation of seven-membered and five-membered cyclometalated platinacycles preceded by Csp2Csp3 reductive elimination

Anderson

Greenberg

Spano

et al. 2016

Journal of Organometallic Chemistry

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A mixture of seven-membered and five-membered platinacycle complexes are eventually formed after a series of substitution, oxidative addition, and reductive elimination reactions between the platinum dimer, cis-[Pt2Me4(µ-SMe2)2] and the naphthyl-derived C^N chelate ligands, (8-XC10H6CH=N-R), X= I, Br; R= phenyl and 4-Cl-benzyl. From the tethered ligand, either an sp 2 C-H bond can be activated forming a five-membered ring or an sp 3 C-H bond can be activated forming a seven-membered ring. All compounds have the imine included in the platinacycle. The ratio of complexes as a function of ring size varies depending on ligand architecture of the chelate ligand and the nature of other ligands in the coordination sphere. The cyclometalated platinum complexes have been characterized by NMR spectroscopy. One complex with a seven-membered ring was characterized crystallographically. Reductive elimination reactions of isolated and/or identified cyclometalated, six-membered platinum(IV) compounds [PtMe2Br{C10H6CH=NCH2(4-ClC6H4)}L] and [PtMe2Br{C10H6CH=N(C6H5)}L] (L = SMe2) to form Csp3-Csp2 bonds, followed by competition between Csp2-H and Csp3-H bond activation are also reported.

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Section: Reactions Of Ligands L1 and L2 With Cis-[pt2me4(µ-sme2)2 Ptasupporting

confidence: 90%

Section: Reactions Of Ligands L1 and L2 With Cis-[pt2me4(µ-sme2)2 Ptamentioning

confidence: 78%

Regioselective competition between the formation of seven-membered and five-membered cyclometalated platinacycles preceded by Csp2Csp3 reductive elimination

Anderson

Greenberg

Spano

et al. 2016

Journal of Organometallic Chemistry

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“… 12 − 18 The additional size and conjugation may enhance the desirable properties of the cyclometalated complexes with benzothiophene-derived ligands. Bismetalated complexes are less studied than their monometalated analogues; 19 − 21 however, perhaps with the additional strong field chelates, C^N ligands may improve the properties of these cyclometaled species. 22 Computational studies on metal compounds have advanced a great deal in the last decade.…”

Section: Introductionmentioning

confidence: 99%

Platinum Complexes from C–H Activation of Sterically Hindered [C^N] Donor Benzothiophene Imine Ligands: Synthesis and Photophysical Properties

et al. 2020

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Primary amines and benzothiophene-3-carboxaldehyde were reacted to give four large, bulky imine ligands. These imine ligands were reacted with a tetramethyl platinum dimer and by heteroatom-assisted C–H activation, both monometalated compounds and bismetalated compounds were synthesized. In all cases, five-membered platinacycles were formed. The compounds were characterized by NMR spectroscopy, and one bismetalated compound was characterized by single-crystal X-ray diffraction. The UV–vis absorption and emission spectra and the excited-state lifetimes were recorded for these complexes. Density functional theory (DFT) and time-dependent-DFT calculations were performed to aid in the assignment of the absorption and emission spectra of the newly synthesized complexes.

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“…The large red-shift of around 200 nm probably indicates emission from a triplet MLCT excited state. 19,[33][34][35][36][37][38] In summary we have synthesized several palladium complexes with N^N^C type pincer ligands. The cyclometalated ring of three of the complexes is the rarer six-membered ring formed by judicious choice of ligand allowing for regioselective formation.…”

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confidence: 99%

Regioselective C–H/C–X activation of naphthyl-derived ligands to form six-membered palladacycles

Anderson

Balema

et al. 2016

Tetrahedron Letters

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Imine N^N^C-type pincer ligands were reacted with palladium(II) acetate and palladium(0) bis(dibenzylideneacetone) and the regioselective C-H and C-X activation was studied. C-X bonds that formed six-membered rings were selectively activated over C-H bonds; in addition sp 2 C-H bonds were selectively activated over sp 3 CH bonds. The formation and regioselectivity of the cyclometalated palladium(II) complexes were characterized by NMR, MS, and XRD. Photoluminescence studies of cyclopalladated complexes were conducted.

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Biscyclometalated platinum complexes with thiophene ligands

Cited by 17 publications

References 67 publications

Regioselective competition between the formation of seven-membered and five-membered cyclometalated platinacycles preceded by Csp2Csp3 reductive elimination

Regioselective competition between the formation of seven-membered and five-membered cyclometalated platinacycles preceded by Csp2Csp3 reductive elimination

Platinum Complexes from C–H Activation of Sterically Hindered [C^N] Donor Benzothiophene Imine Ligands: Synthesis and Photophysical Properties

Regioselective C–H/C–X activation of naphthyl-derived ligands to form six-membered palladacycles

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