Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities
The Pd(II) complexes [Pd(Cp)(L)<sub>n</sub>]<sub>m</sub>[BF<sub>4</sub>]<sub>m</sub> were synthesized via the reaction of cationic acetylacetonate complexes with cyclopentadiene in the presence of BF<sub>3</sub>∙OEt<sub>2</sub>...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-05-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/28/10/4141 |
| _version_ | 1797598885870305280 |
|---|---|
| author | Dmitry S. Suslov Mikhail V. Bykov Marina V. Pakhomova Timur S. Orlov Zorikto D. Abramov Anastasia V. Suchkova Igor A. Ushakov Pavel A. Abramov Alexander S. Novikov |
| author_facet | Dmitry S. Suslov Mikhail V. Bykov Marina V. Pakhomova Timur S. Orlov Zorikto D. Abramov Anastasia V. Suchkova Igor A. Ushakov Pavel A. Abramov Alexander S. Novikov |
| author_sort | Dmitry S. Suslov |
| collection | DOAJ |
| description | The Pd(II) complexes [Pd(Cp)(L)<sub>n</sub>]<sub>m</sub>[BF<sub>4</sub>]<sub>m</sub> were synthesized via the reaction of cationic acetylacetonate complexes with cyclopentadiene in the presence of BF<sub>3</sub>∙OEt<sub>2</sub> (<i>n</i> = 2, <i>m</i> = 1: L = PPh<sub>3</sub> (<b>1</b>), P(<i>p</i>-Tol)<sub>3</sub>, <i>tris</i>(<i>ortho</i>-methoxyphenyl)phosphine (TOMPP), <i>tri</i>-2-furylphosphine, <i>tri</i>-2-thienylphosphine; <i>n</i> = 1, <i>m</i> = 1: L = dppf, dppp (<b>2</b>), dppb (<b>3</b>), 1,5-bis(diphenylphosphino)pentane; <i>n</i> = 1, <i>m</i> = 2 or 3: 1,6-bis(diphenylphosphino)hexane). Complexes <b>1</b>–<b>3</b> were characterized using X-ray diffractometry. The inspection of the crystal structures of the complexes enabled the recognition of (Cp<sup>–</sup>)⋯(Ph-group) and (Cp<sup>–</sup>)⋯(CH<sub>2</sub>-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 (<i>TON</i> up to 2.4∙10<sup>4</sup> mol 1,3-butadiene per mol Pd with chemoselectivity of 82%). Complex [Pd(Cp)(TOMPP)<sub>2</sub>]BF<sub>4</sub> was found to be an efficient catalyst for the polymerization of phenylacetylene (PA) (catalyst activities up to 8.9 × 10<sup>3</sup> g<sub>PA</sub>·(mol<sub>Pd</sub>·h)<sup>−1</sup> were observed) |
| first_indexed | 2024-03-11T03:27:56Z |
| format | Article |
| id | doaj.art-f1de1ad2b1bd4e34bcdfd94085fafcc7 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T03:27:56Z |
| publishDate | 2023-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-f1de1ad2b1bd4e34bcdfd94085fafcc72023-11-18T02:39:51ZengMDPI AGMolecules1420-30492023-05-012810414110.3390/molecules28104141Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic ActivitiesDmitry S. Suslov0Mikhail V. Bykov1Marina V. Pakhomova2Timur S. Orlov3Zorikto D. Abramov4Anastasia V. Suchkova5Igor A. Ushakov6Pavel A. Abramov7Alexander S. Novikov8Research Institute of Oil and Coal Chemical Synthesis, Irkutsk State University, ul. K. Marksa, 1, Irkutsk 664003, RussiaResearch Institute of Oil and Coal Chemical Synthesis, Irkutsk State University, ul. K. Marksa, 1, Irkutsk 664003, RussiaResearch Institute of Oil and Coal Chemical Synthesis, Irkutsk State University, ul. K. Marksa, 1, Irkutsk 664003, RussiaResearch Institute of Oil and Coal Chemical Synthesis, Irkutsk State University, ul. K. Marksa, 1, Irkutsk 664003, RussiaResearch Institute of Oil and Coal Chemical Synthesis, Irkutsk State University, ul. K. Marksa, 1, Irkutsk 664003, RussiaResearch Institute of Oil and Coal Chemical Synthesis, Irkutsk State University, ul. K. Marksa, 1, Irkutsk 664003, RussiaA.E. Favorsky Irkutsk Institute of Chemistry SB RAS, Favorsky St., 1, Irkutsk 664033, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, pr-kt Akad. Lavrentieva, 3, Novosibirsk 630090, RussiaInstitute of Chemistry, Saint Petersburg State University, Universitetskaya Nab., 7/9, Saint Petersburg 199034, RussiaThe Pd(II) complexes [Pd(Cp)(L)<sub>n</sub>]<sub>m</sub>[BF<sub>4</sub>]<sub>m</sub> were synthesized via the reaction of cationic acetylacetonate complexes with cyclopentadiene in the presence of BF<sub>3</sub>∙OEt<sub>2</sub> (<i>n</i> = 2, <i>m</i> = 1: L = PPh<sub>3</sub> (<b>1</b>), P(<i>p</i>-Tol)<sub>3</sub>, <i>tris</i>(<i>ortho</i>-methoxyphenyl)phosphine (TOMPP), <i>tri</i>-2-furylphosphine, <i>tri</i>-2-thienylphosphine; <i>n</i> = 1, <i>m</i> = 1: L = dppf, dppp (<b>2</b>), dppb (<b>3</b>), 1,5-bis(diphenylphosphino)pentane; <i>n</i> = 1, <i>m</i> = 2 or 3: 1,6-bis(diphenylphosphino)hexane). Complexes <b>1</b>–<b>3</b> were characterized using X-ray diffractometry. The inspection of the crystal structures of the complexes enabled the recognition of (Cp<sup>–</sup>)⋯(Ph-group) and (Cp<sup>–</sup>)⋯(CH<sub>2</sub>-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 (<i>TON</i> up to 2.4∙10<sup>4</sup> mol 1,3-butadiene per mol Pd with chemoselectivity of 82%). Complex [Pd(Cp)(TOMPP)<sub>2</sub>]BF<sub>4</sub> was found to be an efficient catalyst for the polymerization of phenylacetylene (PA) (catalyst activities up to 8.9 × 10<sup>3</sup> g<sub>PA</sub>·(mol<sub>Pd</sub>·h)<sup>−1</sup> were observed)https://www.mdpi.com/1420-3049/28/10/4141palladiumcyclopentadienylacetylacetonate1,3-butadienetelomerizationphenylacetylene |
| spellingShingle | Dmitry S. Suslov Mikhail V. Bykov Marina V. Pakhomova Timur S. Orlov Zorikto D. Abramov Anastasia V. Suchkova Igor A. Ushakov Pavel A. Abramov Alexander S. Novikov Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities Molecules palladium cyclopentadienyl acetylacetonate 1,3-butadiene telomerization phenylacetylene |
| title | Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities |
| title_full | Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities |
| title_fullStr | Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities |
| title_full_unstemmed | Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities |
| title_short | Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities |
| title_sort | novel route to cationic palladium ii cyclopentadienyl complexes containing phosphine ligands and their catalytic activities |
| topic | palladium cyclopentadienyl acetylacetonate 1,3-butadiene telomerization phenylacetylene |
| url | https://www.mdpi.com/1420-3049/28/10/4141 |
| work_keys_str_mv | AT dmitryssuslov novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities AT mikhailvbykov novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities AT marinavpakhomova novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities AT timursorlov novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities AT zoriktodabramov novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities AT anastasiavsuchkova novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities AT igoraushakov novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities AT pavelaabramov novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities AT alexandersnovikov novelroutetocationicpalladiumiicyclopentadienylcomplexescontainingphosphineligandsandtheircatalyticactivities |