TY - JOUR

T1 - Lanthanide (Sm, Dy) Complexes with the 9,10-Phenanthrenediimine Redox-Active Ligand: Synthesis and Structures

AU - Sinitsa, D. K.

AU - Akimkina, D. P.

AU - Sukhikh, T. S.

AU - Konchenko, S. N.

AU - Pushkarevsky, N. A.

N1 - This work was supported by the Russian Science Foundation, project 22-23-00983

PY - 2024/5/19

Y1 - 2024/5/19

N2 - Abstract: The complex formation of the redox-active ligand bis(N,N'-2,6-diisopropylphenyl)-9,10-phenanthrenediimine (DippPDI) with alkaline metal (Li, K) and lanthanide (Sm, Dy) cations is studied. The reduction of DippPDI with an alkaline metal excess affords the dianionic form of the ligand (DippPDA2–), which crystallizes with the potassium cation as the coordination polymer [K2(DippPDA)(Thf)3] (Thf is tetrahydrofuran). The reaction of equimolar amounts of the lithium salt with the dianionic form of the ligand and neutral diimine affords the lithium complex with the radical-anion form (DippPSI•–) crystallized as [Li(DippPSI)(Thf)2]. The samarium(III) complex [SmCp*(DippPDA)(Тhf)] (I) is formed by the reduction of DippPDI with samarocene [Sm(Thf)2] (Cp* is pentamethylcyclopentadienide): both the samarium(II) cation and Cp*– anion are oxidized in the reaction. DippPDI does not react with similar ytterbocene. The dysprosium(III) complexes are synthesized by the ion exchange reactions between DyI3(Thf)3.5 and potassium or lithium salt with the DippPDA2– dianion. Similar complexes [Dy(DippPDA)I(Thf)2] (IIThf) and [Dy(DippPDA)I(Thf)(Et2O)] () are formed in the reactions with the potassium salt depending on the solvent used: a THF–hexane or a diethyl ether–n-hexane mixture, respectively. The coordination of the dysprosium cation by the π system of the conjugated fragment of the NCCN ligand is observed in IIThf, whereas in this coordination is absent. The reaction with Li2(DippPDA) affords the binary complex salt [Li(Тhf)3(Et2O)][DyI2(DippPDA)(Тhf)] (III, crystallization from a THF–Et2O mixture). The crystallization from THF gives the [Li(Тhf)4][DyI2(DippPDA)(Thf)] salt (III') containing the same anion as III. The structures of all new complexes are studied by X-ray diffraction (XRD, CIF files CCDC nos. 2260307–2260313).

AB - Abstract: The complex formation of the redox-active ligand bis(N,N'-2,6-diisopropylphenyl)-9,10-phenanthrenediimine (DippPDI) with alkaline metal (Li, K) and lanthanide (Sm, Dy) cations is studied. The reduction of DippPDI with an alkaline metal excess affords the dianionic form of the ligand (DippPDA2–), which crystallizes with the potassium cation as the coordination polymer [K2(DippPDA)(Thf)3] (Thf is tetrahydrofuran). The reaction of equimolar amounts of the lithium salt with the dianionic form of the ligand and neutral diimine affords the lithium complex with the radical-anion form (DippPSI•–) crystallized as [Li(DippPSI)(Thf)2]. The samarium(III) complex [SmCp*(DippPDA)(Тhf)] (I) is formed by the reduction of DippPDI with samarocene [Sm(Thf)2] (Cp* is pentamethylcyclopentadienide): both the samarium(II) cation and Cp*– anion are oxidized in the reaction. DippPDI does not react with similar ytterbocene. The dysprosium(III) complexes are synthesized by the ion exchange reactions between DyI3(Thf)3.5 and potassium or lithium salt with the DippPDA2– dianion. Similar complexes [Dy(DippPDA)I(Thf)2] (IIThf) and [Dy(DippPDA)I(Thf)(Et2O)] () are formed in the reactions with the potassium salt depending on the solvent used: a THF–hexane or a diethyl ether–n-hexane mixture, respectively. The coordination of the dysprosium cation by the π system of the conjugated fragment of the NCCN ligand is observed in IIThf, whereas in this coordination is absent. The reaction with Li2(DippPDA) affords the binary complex salt [Li(Тhf)3(Et2O)][DyI2(DippPDA)(Тhf)] (III, crystallization from a THF–Et2O mixture). The crystallization from THF gives the [Li(Тhf)4][DyI2(DippPDA)(Thf)] salt (III') containing the same anion as III. The structures of all new complexes are studied by X-ray diffraction (XRD, CIF files CCDC nos. 2260307–2260313).

KW - XRD

KW - dysprosium(III)

KW - lanthanocene

KW - phenanthrenediimine

KW - redox-active ligand

KW - samarium(III)

KW - steric properties of ligand

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:001216807500007

UR - https://www.mendeley.com/catalogue/77c017c1-1392-35d0-9052-88d07145d703/

U2 - 10.1134/S1070328423601012

DO - 10.1134/S1070328423601012

M3 - Article

VL - 50

SP - 73

EP - 84

JO - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

JF - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

SN - 1070-3284

IS - 1

ER -