Chromium(III) scorpionate complexes supported by tris(2-pyridyl)phosphine-derived ligands: synthesis, structure, and electrochemical and catalytic properties

Chromium(III) scorpionate complexes supported by tris(2-pyridyl)phosphine-derived ligands: synthesis, structure, and electrochemical and catalytic properties Full article

Journal

Dalton Transactions
ISSN: 1477-9234 , E-ISSN: 1477-9226

Output data

Year: 2026, Volume: 55, Number: 41, Pages: 14788–14795 Pages count : DOI: 10.1039/d6dt01622g

Authors

Ponomarenko Igor A ¹ , Ivanov Andrey S ² , Baranov Andrey Yu ¹ , Komarovskikh Andrey Yu ¹ , Nikitin Mikhail M ² , Kashevskii Alexey V ³ , Amsheev Dmitry Yu ³ , Vilms Alexey I ³ , Bagryanskaya Irina Yu ⁴ , Yakhvarov Dmitry G ^2,5 , Artem’ev Alexander V ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, SB RAS, 3, Lavrentiev Ave., 630090 Novosibirsk, Russia.
2	Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlyovskaya St 18, 420008 Kazan, Russia
3	Irkutsk State University, 1, Karl Marx str., 664003 Irkutsk, Russia
4	Vorozhtsov Novosibirsk Institute of Organic Chemistry, SB RAS, 9, Lavrentiev Ave., 630090 Novosibirsk, Russia
5	Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov St 8, 420088 Kazan, Russia

Funding (1)

The first examples of chromium(III) scorpionate-type complexes supported by tris(2-pyridyl)phosphine derived ligands are reported. Reactions of [Cr(THF)3Cl3] with tris(2-pyridyl)phosphine (Py3P) and its chalcogen derivatives, Py3PS and Py3PSe, afforded the scorpionates [Cr(Py3PX)Cl3] (X = none, S, Se), featuring facial N,N’,N’’-coordination of the ligand. In contrast, reaction with tris(2-pyridyl)phosphine oxide (Py3PO) results in an unexpected ligand transformation, yielding the phosphinite complex [Cr(Py2PO2)(H2O)Cl2] containing the in situ generated [Py2P(O)O]− ligand. X-Ray diffraction analysis established the molecular structures of the complexes, while EPR spectroscopy confirmed the high-spin state of the Cr(III) centres and revealed pronounced rhombic distortion of octahedral Cr3+ ions for the phosphinite derivative. Cyclic voltammetry demonstrates that the PvX functionality significantly influences the redox behaviour of the complexes. Preliminary catalytic studies show that only the phosphine complex [Cr(Py3P)Cl3] is active in ethylene oligomerization and polymerization. Notably, replacing the co-catalyst from MAO to Et3Al dramatically switches the reaction outcome from selective oligomerization to exclusive polymerization. These results establish tris(2-pyridyl)phosphine-derived ligands as a new platform for Cr(III) scorpionate chemistry and provide insight into their structural and functional properties.

Ponomarenko I.A. , Ivanov A.S. , Baranov A.Y. , Komarovskikh A.Y. , Nikitin M.M. , Kashevskii A.V. , Amsheev D.Y. , Vilms A.I. , Bagryanskaya I.Y. , Yakhvarov D.G. , Artem’ev A.V.
Chromium(III) scorpionate complexes supported by tris(2-pyridyl)phosphine-derived ligands: synthesis, structure, and electrochemical and catalytic properties
Dalton Transactions. 2026. V.55. N41. P.14788–14795. DOI: 10.1039/d6dt01622g WOS Scopus OpenAlex

Submitted:	Jul 1, 2026
Accepted:	Oct 6, 2026
Published print:	Oct 27, 2026

≡ Web of science:	WOS:001901906300001
≡ Scopus:	2-s2.0-105053516063
≡ OpenAlex:	W7220832266