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Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand.

作者信息

Ehret Fabian, Filippou Vasileios, Blickle Svenja, Bubrin Martina, Záliš Stanislav, Kaim Wolfgang

机构信息

Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70550, Stuttgart, Germany.

J. Heyrovský Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 3, 18223, Prague, Czech Republic.

出版信息

Chemistry. 2021 Feb 15;27(10):3374-3381. doi: 10.1002/chem.202003636. Epub 2021 Jan 12.

DOI:10.1002/chem.202003636
PMID:32959415
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7986709/
Abstract

Reaction of [Pt(DMSO) Cl ] or [Pd(MeCN) Cl ] with the electron-rich LH=N,N'-bis(4-dimethylaminophenyl)ethanimidamide yielded mononuclear [PtL ] (1) but dinuclear [Pd L ] (2), a paddle-wheel complex. The neutral compounds were characterized through experiments (crystal structures, electrochemistry, UV-vis-NIR spectroscopy, magnetic resonance) and TD-DFT calculations as metal(II) species with noninnocent ligands L . The reversibly accessible cations [PtL ] and [Pd L ] were also studied, the latter as [Pd L ][B{3,5-(CF ) C H } ] single crystals. Experimental and computational investigations were directed at the elucidation of the electronic structures, establishing the correct oxidation states within the alternatives [Pt (L ) ] or [Pt (L ) ], [Pt (L ) ] or [Pt (L ) ] , [(Pd ) (μ-L ) ] or [(Pd ) (μ-L ) ], and [(Pd ) (μ-L ) ] or [(Pd ) (μ-L ) ] . In each case, the first alternative was shown to be most appropriate. Remarkable results include the preference of platinum for mononuclear planar [PtL ] with an N-Pt-N bite angle of 62.8(2)° in contrast to [Pd L ], and the dimetal (Pd →Pd ) instead of ligand (L →L ) oxidation of the dinuclear palladium compound.

摘要
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/8a6b2add80db/CHEM-27-3374-g014.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/e8e1f0dd9a22/CHEM-27-3374-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/ab81ea33da4d/CHEM-27-3374-g012.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/8a6b2add80db/CHEM-27-3374-g014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/99622161d706/CHEM-27-3374-g015.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/5dc178106825/CHEM-27-3374-g016.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/a3c9febc1376/CHEM-27-3374-g017.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/c0565a690ba2/CHEM-27-3374-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/ba83dc039414/CHEM-27-3374-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/fb0d16e71d9a/CHEM-27-3374-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/e155bdd7a329/CHEM-27-3374-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/2d5c4bea15c9/CHEM-27-3374-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/47ce2eaff18f/CHEM-27-3374-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/c1db2abd379b/CHEM-27-3374-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/0bb59e7eee1c/CHEM-27-3374-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/ed3ddf78414f/CHEM-27-3374-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/70a876dcb47f/CHEM-27-3374-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/e8e1f0dd9a22/CHEM-27-3374-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/ab81ea33da4d/CHEM-27-3374-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/5d4ffbc0ebab/CHEM-27-3374-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/471b/7986709/8a6b2add80db/CHEM-27-3374-g014.jpg

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