Unknown

Dataset Information

0

A Trinuclear Gadolinium Cluster with a Three-Center One-Electron Bond and an S = 11 Ground State.


ABSTRACT: The recent discovery of metal-metal bonding and valence delocalization in the dilanthanide complexes (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Y, Gd, Tb, Dy) opened up the prospect of harnessing the 4fn5dz21 electron configurations of non-traditional divalent lanthanide ions to access molecules with novel bonding motifs and magnetism. Here, we report the trinuclear mixed-valence clusters (CpiPr5)3Ln3H3I2 (1-Ln, Ln = Y, Gd), which were synthesized via potassium graphite reduction of the trivalent clusters (CpiPr5)3Ln3H3I3. Structural, computational, and spectroscopic analyses support valence delocalization in 1-Ln resulting from a three-center, one-electron σ bond formed from the 4dz2 and 5dz2 orbitals on Y and Gd, respectively. Dc magnetic susceptibility data obtained for 1-Gd reveal that valence delocalization engenders strong parallel alignment of the σ-bonding electron and the 4f electrons of each gadolinium center to afford a high-spin ground state of S = 11. Notably, this represents the first clear instance of metal-metal bonding in a molecular trilanthanide complex, and the large spin-spin exchange constant of J = 168(1) cm-1 determined for 1-Gd is only the second largest coupling constant characterized to date for a molecular lanthanide compound.

SUBMITTER: McClain KR 

PROVIDER: S-EPMC10141408 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature

altmetric image

Publications

A Trinuclear Gadolinium Cluster with a Three-Center One-Electron Bond and an <i>S</i> = 11 Ground State.

McClain K Randall KR   Kwon Hyunchul H   Chakarawet Khetpakorn K   Nabi Rizwan R   Kragskow Jon G C JGC   Chilton Nicholas F NF   Britt R David RD   Long Jeffrey R JR   Harvey Benjamin G BG  

Journal of the American Chemical Society 20230417 16


The recent discovery of metal-metal bonding and valence delocalization in the dilanthanide complexes (Cp<sup>iPr5</sup>)<sub>2</sub>Ln<sub>2</sub>I<sub>3</sub> (Cp<sup>iPr5</sup> = pentaisopropylcyclopentadienyl; Ln = Y, Gd, Tb, Dy) opened up the prospect of harnessing the 4f<sup><i>n</i></sup>5d<sub>z<sup>2</sup></sub><sup>1</sup> electron configurations of non-traditional divalent lanthanide ions to access molecules with novel bonding motifs and magnetism. Here, we report the trinuclear mixed-  ...[more]

Similar Datasets

| S-EPMC8811720 | biostudies-literature
| S-EPMC6776552 | biostudies-literature
| S-EPMC11350594 | biostudies-literature
| S-EPMC11744793 | biostudies-literature
| S-EPMC11492808 | biostudies-literature
| S-EPMC10510625 | biostudies-literature
2023-09-06 | GSE222058 | GEO
| S-EPMC11500291 | biostudies-literature
| S-EPMC8153215 | biostudies-literature
2025-05-06 | PXD039213 | Pride