A π-Carbazolyl Dy(III) Half-Sandwich Complex Showing Single-Molecule-Magnet Behavior
作者:Jérôme Long、Alexander N. Selikhov、Konstantin A. Lyssenko、Yannick Guari、Joulia Larionova、Alexander A. Trifonov
DOI:10.1021/acs.organomet.0c00426
日期:2020.8.10
investigations of the new Dy3+ heteroleptic complex [Dy(tBu4Carb)(o-Me2NC6H4CH2)2]·C7H8 (1; tBu4Carb = 1,3,6,8-tetra-tert-butyl-9H-carbazole, o-Me2NC6H4CH2)2 = o-N,N-dimethylaminobenzyl). The carbazolyl ligand exhibits an unprecedented η5 π interaction with the magnetically anisotropic dysprosium(III) ion, resulting in a zero-field single-molecule-magnetbehavior.
我们报告了新型Dy 3+杂配物[Dy(t Bu 4 Carb)(o -Me 2 NC 6 H 4 CH 2)2 ]·C 7 H 8(1 ; t Bu )的合成,结构和磁性研究。4碳水化合物= 1,3,6,8-四-叔丁基- 9 ħ -咔唑,ö -Me 2 NC 6 H ^ 4 CH 2)2 = ø - ñ,N-二甲基氨基苄基)。咔唑配体显示出了前所未有的η 5 π相互作用与磁各向异性镝(III)离子,从而产生零场单分子磁铁的行为。
Base‐Free Alkoxide Dysprosium(III) Complexes with an Unusual Tetraphenylborate Coordination: Study of the Slow Relaxation of the Magnetization
作者:Jérôme Long、Alexander N. Selikhov、Anton V. Cherkasov、Yulia V. Nelyubina、Fabrice Salles、Yannick Guari、Joulia Larionova、Alexander A. Trifonov
DOI:10.1002/ejic.202200397
日期:2022.10.26
solvent-free dysprosium(III) complexes of formula showing an unsual tetraphenylborate binding due to the use of sterically demanding alkoxide ligands. Investigations of the magnetic properties for 1 in line with theoretical calculations reveal a field-induced slow relaxation of the magnetization making it one of the rare examples of Single-Molecule Magnet with coordinated tetraphenylborate.
Reactivity of Traditional Metal–Carbon (Alkyl) versus Nontraditional Metal–Carbon (Cage) Bonds in Organo-Rare-Earth Metal Complexes [η<sup>5</sup>:σ-(C<sub>9</sub>H<sub>6</sub>)(C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)]Ln(CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>-<i>o</i>-NMe<sub>2</sub>)(THF)<sub>2</sub>
作者:Jingying Yang、Zuowei Xie
DOI:10.1021/om501212e
日期:2015.6.8
Equimolar reaction of 1-indenyl-1,2-carborane with Ln(CH2C6H4-o-NMe2)(3) in THF gave highly constrained-geometry complexes [eta(5):sigma-(C9H6)C2B10H10]Ln(CH2C6H4-o-NMe2)(THF)(2) (Ln = Y (1a), Gd (1b), Dy (1c)). They reacted with RN=C=NR or 2,6-Me2C6H3NCS to generate the Ln-C-alkyl insertion products [eta(5):sigma-(C9H6)C2B10H10]Ln-(eta(2)(RN)(2)C(CH2C6H4-o-NMe2)](THF) (R = TMS, Ln = Y (2a), Gd (2b); R = Bu-t, Ln = Y (2a), Gd (2b); R = Bu-t, Ln = Y (3a)) or [eta(5):sigma-(C9H6)C2B10H10]Dy[eta(2)-(2,6-Me2C6H3)NC(CH2C6H4-o-NMe2)S](THF)(2) (4c). Treatment of 2a with I equiv of R'N=C=NR' to give the Y-C-cage insertion complexes [eta(5):sigma-(C9H6)N(R')C(=NR')}C2B10H10]Y[eta(2)-(TMS)N}(2)C(CH2C6H4-o-NMe2)] (R' = Cy (5a), Pr-i (6a)). Similarly, unsaturated compounds Ph2C=C=O and PY2C=O (Py = 2-pyridyl) also inserted into the Y-C-cage bond in 2a to yield [eta(5):sigma-(C9H6)OC(=CPh2)}C2B10H10]Y[eta(2)-(TMS)N}(2)C(CH2C6H4-o-NMe2)] (7a) and [eta(5):sigma-(C9H6)OC(Py)(2)}C2B10H10]Y[eta(2)-(TMS)N)}(2)C(CH2C6H4-o-NMe2)](THF) (8a), respectively. In sharp contrast to the earlier reports that the nontraditional metal-C-cage sigma bonds in metal carboranyl complexes are generally inert toward electrophiles, the insertion of unsaturated molecules into the Y-C-cage sigma bond in 2a represents the first example of this type of reactions. These results shed some light on how to activate the nontraditional metal-carbon (cage) bonds in metal-Carboranyl complexes. All new complexes were characterized by spectroscopic techniques and elemental analyses. Some were further confirmed by single-crystal X-ray analyses.