Imposing high-symmetry and tuneable geometry on lanthanide centres with chelating Pt and Pd metalloligands

Chemical Science
Mikkel A SørensenJesper Bendix

Abstract

Exploitation of HSAB preferences allows for high-yield, one-pot syntheses of lanthanide complexes chelated by two Pd or Pt metalloligands, [MII(SAc)4]2- (SAc- = thioacetate, M = Pd, Pt). The resulting complexes with 8 oxygen donors surrounding the lanthanides can be isolated in crystallographically tetragonal environments as either [NEt4]+ (space group: P4/mcc) or [PPh4]+ (space group: P4/n) salts. In the case of M = Pt, the complete series of lanthanide complexes has been structurally characterized as the [NEt4]+ salts (except for Ln = Pm), while the [PPh4]+ salts have been structurally characterized for Ln = Gd-Er, Y. For M = Pd, selected lanthanide complexes have been structurally characterized as both salts. The only significant structural difference between salts of the two counter ions is the resulting twist angle connecting tetragonal prismatic and tetragonal anti-prismatic configurations, with the [PPh4]+ salts approaching ideal D4d symmetry very closely (φ = 44.52-44.61°) while the [NEt4]+ salts exhibit intermediate twist angles in the interval φ = 17.28-27.41°, the twist increasing as the complete 4f series is traversed. Static magnetic properties for the latter half of the lanthanide series are found to agree well in...Continue Reading

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Citations

Sep 18, 2018·Chemical Communications : Chem Comm·Mauro Perfetti, Jesper Bendix
Sep 29, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Takefumi YoshidaMasahiro Yamashita
Jul 6, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Angeliki A AthanasopoulouEva Rentschler
Feb 12, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Takefumi YoshidaMasahiro Yamashita
Aug 20, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Gabriela HandzlikDawid Pinkowicz
Aug 9, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Anders H PedersenEuan K Brechin
Mar 31, 2018·Nature Communications·Mikkel A SørensenJesper Bendix
Aug 23, 2018·Chemical Communications : Chem Comm·Dimitris I AlexandropoulosKim R Dunbar
Jul 4, 2017·Chemistry : a European Journal·Takefumi YoshidaMasahiro Yamashita
Jun 4, 2021·Chemical Reviews·Pierre Braunstein, Andreas A Danopoulos
Jan 30, 2020·The Journal of Physical Chemistry Letters·Gabriela HandzlikDawid Pinkowicz
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Dec 12, 2019·Inorganic Chemistry·Niels A BondeMauro Perfetti
Jan 17, 2020·Inorganic Chemistry·Andreas M ThielJacob Overgaard
Oct 30, 2020·Inorganic Chemistry·Mauro PerfettiKira E Vostrikova

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Methods Mentioned

BETA
X-ray
electron paramagnetic resonance

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