Chelating Borohydrides for Lanthanides and Actinides: Structures, Mechanochemistry, and Case Studies with Phosphinodiboranates

Fetrow, Taylor V.; Bhowmick, Rina; Achazi, Andreas J.; Blake, Anastasia V.; Eckstrom, Francesca D.; Vlaisavljevich, Bess; Daly, Scott R.

doi:10.1021/acs.inorgchem.9b01628

Title: Chelating Borohydrides for Lanthanides and Actinides: Structures, Mechanochemistry, and Case Studies with Phosphinodiboranates

Journal Article · Fri Aug 30 00:00:00 EDT 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b01628· OSTI ID:1902047

Fetrow, Taylor V. ^[1]; Bhowmick, Rina ^[2]; Achazi, Andreas J. ^[2]; Blake, Anastasia V. ^[1]; Eckstrom, Francesca D. ^[1]; Vlaisavljevich, Bess ^[2];

^[1]

Univ. of Iowa, Iowa City, IA (United States)
Univ. of South Dakota, Vermillion, SD (United States)

In this Forum Article, we review the development of chelating borohydride ligands called aminodiboranates (H₃BNR₂BH₃^–) and phosphinodiboranates (H₃BPR₂BH₃^–) for the synthesis of trivalent f-element complexes. The advantages and history of using mechanochemistry to prepare molecular borohydride complexes are described along with new results demonstrating the mechanochemical synthesis of M₂(H₃BP^tBu₂BH₃)₆, where M = U, Nd, Tb, Er, and Lu (1–5). Multinuclear NMR, IR, and single-crystal X-ray diffraction data are reported for 1–5 alongside complementary density functional theory calculations to reveal differences in their structure and reactivity with and without tetrahydrofuran. The results demonstrate how mechanochemistry can be used to access f-element complexes with chelating borohydrides in improved and reproducible yields, which is an important step toward investigating the properties of lanthanide and actinide phosphinodiboranate complexes with different phosphorus substituents. Furthermore, the relevance of these results is contextualized by a discussion of structural factors known to influence the volatility of f-element borohydrides and applications that require the development of volatile f-element complexes.

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Research Organization:: Univ. of Iowa, Iowa City, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019426

OSTI ID:: 1902047

Journal Information:: Inorganic Chemistry, Vol. 59, Issue 1; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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