TY - JOUR

T1 - Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities

AU - Suslov, Dmitry S.

AU - Bykov, Mikhail V.

AU - Pakhomova, Marina V.

AU - Orlov, Timur S.

AU - Abramov, Zorikto D.

AU - Suchkova, Anastasia V.

AU - Ushakov, Igor A.

AU - Abramov, Pavel A.

AU - Novikov, Alexander S.

N1 - Suslov, D.S.; Bykov, M.V.; Pakhomova, M.V.; Orlov, T.S.; Abramov, Z.D.; Suchkova, A.V.; Ushakov, I.A.; Abramov, P.A.; Novikov, A.S. Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities. Molecules 2023, 28, 4141. https://doi.org/10.3390/molecules28104141

PY - 2023/5/17

Y1 - 2023/5/17

N2 - 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)

AB - 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)

KW - palladium

KW - cyclopentadienyl

KW - acetylacetonate

KW - 1,3-butadienes

KW - telomerization

KW - Phenylacetylene

KW - phenylacetylene

KW - 1,3-butadiene

UR - https://www.mendeley.com/catalogue/72f7f442-f04e-363a-9dc1-e86ec649ae5f/

U2 - 10.3390/molecules28104141

DO - 10.3390/molecules28104141

M3 - Article

VL - 28

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 10

M1 - 4141

ER -