TY - JOUR

T1 - Tris(2-pyrimidyl)- and tris(5-pyrimidyl)phosphines: new multidentate ligands with diverse coordination chemistry

AU - Baranov, Andrey Yu

AU - Kuzmin, Anton V.

AU - Sukhikh, Taisia S.

AU - Mostovich, Evgeny A.

AU - Sadykov, Evgeny Kh

AU - Artem'ev, Alexander V.

PY - 2026

Y1 - 2026

N2 - Tris(2-pyrimidyl)- and tris(5-pyrimidyl)phosphines, previously inaccessible multidentate ligands, have been synthesized and introduced into coordination chemistry. Theoretical studies indicate that both ligands are weak σ-donors and strong π-acceptors, exhibiting electronic properties comparable to those of trialkyl phosphites. Positional isomerism of the pyrimidyl groups induces a pronounced difference in steric profile, with the 5-isomer adopting a more open conformation and the 2-isomer a significantly more compact geometry, reflected in their Tolman cone angles of 157° and 148°, respectively. Reactions with Cu(i), Cu(ii), Ag(i), Au(i), Co(ii), and Pt(ii) salts afforded a series of molecular complexes together with 1D and 2D coordination polymers. Tris(5-pyrimidyl)phosphine acts predominantly as a P-monodentate or P,N-/N,N′-bridging ligand, yielding extended frameworks, whereas tris(2-pyrimidyl)phosphine forms both discrete complexes and coordination polymers through P,N,N′- and P,N,N′,N″-modes. Selected Cu(i) and Ag(i) complexes exhibit short-lived luminescence with emission maxima between 460 and 605 nm. These findings demonstrate the potential of symmetric tris(pyrimidyl)phosphines as versatile ligands for coordination chemistry.

AB - Tris(2-pyrimidyl)- and tris(5-pyrimidyl)phosphines, previously inaccessible multidentate ligands, have been synthesized and introduced into coordination chemistry. Theoretical studies indicate that both ligands are weak σ-donors and strong π-acceptors, exhibiting electronic properties comparable to those of trialkyl phosphites. Positional isomerism of the pyrimidyl groups induces a pronounced difference in steric profile, with the 5-isomer adopting a more open conformation and the 2-isomer a significantly more compact geometry, reflected in their Tolman cone angles of 157° and 148°, respectively. Reactions with Cu(i), Cu(ii), Ag(i), Au(i), Co(ii), and Pt(ii) salts afforded a series of molecular complexes together with 1D and 2D coordination polymers. Tris(5-pyrimidyl)phosphine acts predominantly as a P-monodentate or P,N-/N,N′-bridging ligand, yielding extended frameworks, whereas tris(2-pyrimidyl)phosphine forms both discrete complexes and coordination polymers through P,N,N′- and P,N,N′,N″-modes. Selected Cu(i) and Ag(i) complexes exhibit short-lived luminescence with emission maxima between 460 and 605 nm. These findings demonstrate the potential of symmetric tris(pyrimidyl)phosphines as versatile ligands for coordination chemistry.

UR - https://www.scopus.com/pages/publications/105052594750

UR - https://www.mendeley.com/catalogue/e834e75d-b197-3e32-adef-ba350e471b70/

U2 - 10.1039/d6dt01917j

DO - 10.1039/d6dt01917j

M3 - Article

C2 - 42825433

VL - 55

SP - 14494

EP - 14506

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 40

ER -