Tris(carbene)borates; alternatives to cyclopentadienyls in organolanthanide chemistry

Price, Amy N.; Gupta, Ankur K.; de Jong, Wibe A.; Arnold, Polly L.

doi:10.1039/d3dt00718a

Tris(carbene)borates; alternatives to cyclopentadienyls in organolanthanide chemistry

Journal Article · Tue Apr 18 00:00:00 EDT 2023 · Dalton Transactions

DOI:https://doi.org/10.1039/d3dt00718a· OSTI ID:2008313

Price, Amy N. ^[1]; ^[2]; ^[2]; ^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

The chemistry of the tris-carbene anion phenyltris(3-alkyl-imidazoline-2-yliden-1-yl)borate, [C3^Me]^- ligand, is initiated for f-block metal cations. Neutral, molecular complexes of the form Ln(C3)₂I are formed for cerium(III), while a separated ion pair [Ln(C3)₂]I forms for ytterbium(III). DFT/QTAIM computational analyses of the complexes and related tridentate tris(pyrazolyl)borate (Tp) – supported analogs demonstrates the anticipated strength of the σ donation and confirms greater covalency in the metal–carbon bonds of the [C3^Me]^- complexes in comparison with those in the Tp^Me,Me complexes. The DFT calculations demonstrate the crucial role of THF solvent in accurately reproducing the contrasting molecular and ion-pair geometries observed experimentally for the Ce and Yb complexes.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); NIH

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2008313

Alternate ID(s):: OSTI ID: 1970405

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 17 Vol. 52; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Tris(carbene)borates; alternatives to cyclopentadienyls in organolanthanide chemistry

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