TY - JOUR

T1 - Preparation of trans,trans-[Pt(py)2(N3)2(OH)2] via Photoinduced Reactivity of [Pt(NO3)6]2- Anion

AU - Zazulya, Alexei

AU - Berdyugin, Semen

AU - Tkachev, Sergey

AU - Lagunova, Varvara

AU - Sheven, Dmitriy

AU - Abramov, Pavel

AU - Glebov, Evgeni

AU - Vasilchenko, Danila

N1 - The part of this work including the photoinduced formation of [PtL4](NO3)2 and the (Bu4N)2[Pt(NO3)6] photochemistry study was supported by the Russian Science Foundation (RSF grant no 23-13-00226). The part of the work devoted to the crystal structure determination, kinetic study of [Pt(py)4]2+ anation, and synthesis of Pt(IV) azido complexes was carried out with financial support of the Ministry of Science and Higher Education of the Russian Federation, project no. 121031700315-2. The authors deeply thank the XRD Facility of NIIC SB RAS for the single-crystal data collection.

PY - 2025/2

Y1 - 2025/2

N2 - The photoinduced reaction of [Pt(NO3)6]2- with pyridine or its derivatives (L) was found to result in the formation of [PtL4](NO3)2 salts in high yield. This transformation was successfully probed for methyl- and carboxyethyl-substituted pyridines, and the corresponding [PtL4](NO3)2 salts were isolated and fully characterized using single-crystal X-ray diffraction (SCXRD). Anation of the [Pt(py)4]2+ cationic complex with N3- was studied by 1H NMR spectroscopy in aqueous and water/dimethyl sulfoxide solutions of [Pt(py)4](NO3)2. A mixture of cis- and trans-[Pt(py)2(N3)2] complexes was determined as the final product of this interaction with the domination of the trans-isomer (cis to trans ratio is about 1:8) due to its preferable formation from the transient [Pt(py)3(N3)]+ cationic complex. The difference observed for the experimentally determined activation parameters of trans- and cis-paths of anation was supported by DFT calculations. Finally, the new three-stage Ag-free synthetic procedure for the preparation of the trans,trans-[Pt(py)2(N3)2(OH)2] prodrug (potential agent for the photodynamic anticancer therapy) was found using (i) light-induced formation of [Pt(py)4](NO3)2 from (Bu4N)2[Pt(NO3)6] followed by (ii) anation of [Pt(py)4]2+ with azide and (iii) accomplished by oxidation of the resulting mixture of cis- and trans-[Pt(py)2(N3)2] with H2O2. Efficient separation of cis,trans-[Pt(py)2(OH)2(N3)2] and trans,trans-[Pt(py)2(N3)2(OH)2] produced at the last stage was achieved by simple recrystallization from water.

AB - The photoinduced reaction of [Pt(NO3)6]2- with pyridine or its derivatives (L) was found to result in the formation of [PtL4](NO3)2 salts in high yield. This transformation was successfully probed for methyl- and carboxyethyl-substituted pyridines, and the corresponding [PtL4](NO3)2 salts were isolated and fully characterized using single-crystal X-ray diffraction (SCXRD). Anation of the [Pt(py)4]2+ cationic complex with N3- was studied by 1H NMR spectroscopy in aqueous and water/dimethyl sulfoxide solutions of [Pt(py)4](NO3)2. A mixture of cis- and trans-[Pt(py)2(N3)2] complexes was determined as the final product of this interaction with the domination of the trans-isomer (cis to trans ratio is about 1:8) due to its preferable formation from the transient [Pt(py)3(N3)]+ cationic complex. The difference observed for the experimentally determined activation parameters of trans- and cis-paths of anation was supported by DFT calculations. Finally, the new three-stage Ag-free synthetic procedure for the preparation of the trans,trans-[Pt(py)2(N3)2(OH)2] prodrug (potential agent for the photodynamic anticancer therapy) was found using (i) light-induced formation of [Pt(py)4](NO3)2 from (Bu4N)2[Pt(NO3)6] followed by (ii) anation of [Pt(py)4]2+ with azide and (iii) accomplished by oxidation of the resulting mixture of cis- and trans-[Pt(py)2(N3)2] with H2O2. Efficient separation of cis,trans-[Pt(py)2(OH)2(N3)2] and trans,trans-[Pt(py)2(N3)2(OH)2] produced at the last stage was achieved by simple recrystallization from water.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85216485258&origin=inward&txGid=3afc39beb5b1214b3f96c74622f773aa

UR - https://www.mendeley.com/catalogue/20909fca-7190-38bb-87be-22c1e8e3243a/

U2 - 10.1021/acs.inorgchem.4c04536

DO - 10.1021/acs.inorgchem.4c04536

M3 - Article

C2 - 39874060

VL - 64

SP - 2336

EP - 2347

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

M1 - 18

ER -