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

K.R. McClain, H. Kwon, K. Chakarawet, R. Nabi, J.G.C. Kragskow, N.F. Chilton, R.D. Britt, Jeffrey R. Long, B.G. Harvey

Research output: Contribution to journalArticlepeer-review

18 Citations (SciVal)

Abstract

The recent discovery of metal−metal bonding and valence
delocalization in the dilanthanide complexes (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopro-
pylcyclopentadienyl; 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.
Original languageEnglish
Pages (from-to)8996-9002
JournalJournal of the American Chemical Society
Volume145
Early online date17 Apr 2023
DOIs
Publication statusPublished - 26 Apr 2023

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