On the usability of salt metathesis reactions for the synthesis of sterically crowded tris-formamidinate Ln(iii) complexes: success and limits. Spontaneous reduction of Eu(iii) to Eu(ii)

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On the usability of salt metathesis reactions for the synthesis of sterically crowded tris-formamidinate Ln(iii) complexes: success and limits. Spontaneous reduction of Eu(iii) to Eu(ii). / Bashirov, Denis A.; Kolybalov, Dmitry S.; Mironova, Olga A. et al.

In: New Journal of Chemistry, Vol. 46, No. 25, 24.05.2022, p. 11994-12001.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{90538d3e96fe4647bc1fdc58fde84bbe,

title = "On the usability of salt metathesis reactions for the synthesis of sterically crowded tris-formamidinate Ln(iii) complexes: success and limits. Spontaneous reduction of Eu(iii) to Eu(ii)",

abstract = "Homoleptic [Ln(FormDipp)3] (FormDipp− = CH(NDipp)2− (Dipp = 2,6-diisopropylphenyl), Ln = Nd, Eu) complexes bearing three bulky formamidinate ligands were successfully obtained using the salt metathesis approach, viz. the reaction of [Ln(FormDipp)2Cl(thf)n] (Ln = Nd (n = 2), Ln = Eu (n = 1)) with K(FormDipp) in toluene at 100 °C. This method is not useful for the Ln smaller than Eu: all attempts to realize it for Gd and Tb were unsuccessful. In the case of Eu, the tris-formamidinate complex was obtained in toluene, but in a thf/toluene mixture, a spontaneous reduction of Eu(iii) to Eu(ii) leading to the formation of [Eu(FormDipp)2(thf)2] was observed. The Eu(iii) to Eu(ii) conversion is rather sterically induced. UV-Vis spectroscopy monitoring of the reaction indicates it to be a zero-order process. Possible routes of the reaction are proposed.",

author = "Bashirov, {Denis A.} and Kolybalov, {Dmitry S.} and Mironova, {Olga A.} and Sukhikh, {Taisiya S.} and Konchenko, {Sergey N.}",

note = "Funding Information: The work was supported by the Ministry of Science and Higher Education of the Russian Federation (No. 121031700313-8 and 121031700321-3). Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry",

year = "2022",

month = may,

day = "24",

doi = "10.1039/d2nj01589g",

language = "English",

volume = "46",

pages = "11994--12001",

journal = "New Journal of Chemistry",

issn = "1144-0546",

publisher = "ROYAL SOC CHEMISTRY",

number = "25",

}

RIS

TY - JOUR

T1 - On the usability of salt metathesis reactions for the synthesis of sterically crowded tris-formamidinate Ln(iii) complexes: success and limits. Spontaneous reduction of Eu(iii) to Eu(ii)

AU - Bashirov, Denis A.

AU - Kolybalov, Dmitry S.

AU - Mironova, Olga A.

AU - Sukhikh, Taisiya S.

AU - Konchenko, Sergey N.

N1 - Funding Information: The work was supported by the Ministry of Science and Higher Education of the Russian Federation (No. 121031700313-8 and 121031700321-3). Publisher Copyright: © 2022 The Royal Society of Chemistry

PY - 2022/5/24

Y1 - 2022/5/24

N2 - Homoleptic [Ln(FormDipp)3] (FormDipp− = CH(NDipp)2− (Dipp = 2,6-diisopropylphenyl), Ln = Nd, Eu) complexes bearing three bulky formamidinate ligands were successfully obtained using the salt metathesis approach, viz. the reaction of [Ln(FormDipp)2Cl(thf)n] (Ln = Nd (n = 2), Ln = Eu (n = 1)) with K(FormDipp) in toluene at 100 °C. This method is not useful for the Ln smaller than Eu: all attempts to realize it for Gd and Tb were unsuccessful. In the case of Eu, the tris-formamidinate complex was obtained in toluene, but in a thf/toluene mixture, a spontaneous reduction of Eu(iii) to Eu(ii) leading to the formation of [Eu(FormDipp)2(thf)2] was observed. The Eu(iii) to Eu(ii) conversion is rather sterically induced. UV-Vis spectroscopy monitoring of the reaction indicates it to be a zero-order process. Possible routes of the reaction are proposed.

AB - Homoleptic [Ln(FormDipp)3] (FormDipp− = CH(NDipp)2− (Dipp = 2,6-diisopropylphenyl), Ln = Nd, Eu) complexes bearing three bulky formamidinate ligands were successfully obtained using the salt metathesis approach, viz. the reaction of [Ln(FormDipp)2Cl(thf)n] (Ln = Nd (n = 2), Ln = Eu (n = 1)) with K(FormDipp) in toluene at 100 °C. This method is not useful for the Ln smaller than Eu: all attempts to realize it for Gd and Tb were unsuccessful. In the case of Eu, the tris-formamidinate complex was obtained in toluene, but in a thf/toluene mixture, a spontaneous reduction of Eu(iii) to Eu(ii) leading to the formation of [Eu(FormDipp)2(thf)2] was observed. The Eu(iii) to Eu(ii) conversion is rather sterically induced. UV-Vis spectroscopy monitoring of the reaction indicates it to be a zero-order process. Possible routes of the reaction are proposed.

UR - http://www.scopus.com/inward/record.url?scp=85131968280&partnerID=8YFLogxK

U2 - 10.1039/d2nj01589g

DO - 10.1039/d2nj01589g

M3 - Article

AN - SCOPUS:85131968280

VL - 46

SP - 11994

EP - 12001

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 25

ER -

ID: 36433933