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Novel Route to Cationic Palladium(II)-Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities.
| Content Provider | Europe PMC |
|---|---|
| Author | Suslov, Dmitry S. Bykov, Mikhail V. Pakhomova, Marina V. Orlov, Timur S. Abramov, Zorikto D. Suchkova, Anastasia V. Ushakov, Igor A. Abramov, Pavel A. Novikov, Alexander S. |
| Editor | Yuan, Shaojun Zhao, Yuchao |
| Copyright Year | 2023 |
| Abstract | The Pd(II) complexes [Pd(Cp)(L)n]m[BF4]m were synthesized via the reaction of cationic acetylacetonate complexes with cyclopentadiene in the presence of BF3∙OEt2 (n = 2, m = 1: L = PPh3 (1), P(p-Tol)3, tris(ortho-methoxyphenyl)phosphine (TOMPP), tri-2-furylphosphine, tri-2-thienylphosphine; n = 1, m = 1: L = dppf, dppp (2), dppb (3), 1,5-bis(diphenylphosphino)pentane; n = 1, m = 2 or 3: 1,6-bis(diphenylphosphino)hexane). Complexes 1-3 were characterized using X-ray diffractometry. The inspection of the crystal structures of the complexes enabled the recognition of (Cp-)⋯(Ph-group) and (Cp-)⋯(CH2-group) interactions, which are of C-H…π nature. The presence of these interactions was confirmed theoretically via DFT calculations using QTAIM analysis. The intermolecular interactions in the X-ray structures are non-covalent in origin with an estimated energy of 0.3-1.6 kcal/mol. The cationic palladium catalyst precursors with monophosphines were found to be active catalysts for the telomerization of 1,3-butadiene with methanol (TON up to 2.4∙104 mol 1,3-butadiene per mol Pd with chemoselectivity of 82%). Complex [Pd(Cp)(TOMPP)2]BF4 was found to be an efficient catalyst for the polymerization of phenylacetylene (PA) (catalyst activities up to 8.9 × 103 gPA·(molPd·h)-1 were observed). |
| Journal | Molecules |
| Volume Number | 28 |
| DOI | 10.3390/molecules28104141 |
| PubMed Central reference number | PMC10221666 |
| Issue Number | 10 |
| PubMed reference number | 37241882 |
| e-ISSN | 14203049 |
| Language | English |
| Publisher | Molecular Diversity Preservation International (MDPI) |
| Publisher Date | 2023-05-17 |
| Access Restriction | Open |
| Subject Keyword | palladium cyclopentadienyl acetylacetonate 1,3-butadiene telomerization phenylacetylene |
| Content Type | Text |
| Resource Type | Article |
| Subject | Physical and Theoretical Chemistry Medicine Chemistry Drug Discovery Pharmaceutical Science Analytical Chemistry Molecular Medicine Organic Chemistry |
