Issue 19, 2020

Synthesis and characterisation of light lanthanide bis-phospholyl borohydride complexes

Abstract

Organometallic lanthanide (Ln) chemistry is dominated by complexes that contain substituted cyclopentadienyl (CpR) ligands. Closely related phospholyls have received less attention, and although they have proven utility in stabilising low oxidation state Ln complexes the trivalent Ln chemistry of these ligands is limited in comparison. Herein, we synthesise two families of heteroleptic Ln3+ complexes, [Ln(Htp)2(μ-BH4)]2 (Htp = 2,5-di-tert-butylphospholyl; 1-Ln; Ln = La, Ce, Nd, Sm), and [[Ln(Htp)2(μ-BH4)2K(S)]n (2-Ln, Ln = La, Ce, S = 2 DME, n = 2; 3-Ce, Ln = Ce, S = Et2O and THF, n = ∞) via the reactions of parent [Ln(BH4)3(THF)3.5] with K(Htp), to investigate differences between Ln complexes with substituted phospholyl ligands and analogous CpR complexes. Complexes 1–3-Ln were characterised as appropriate by single crystal XRD, SQUID magnetometry, elemental analysis, multinuclear NMR, ATR-IR and UV-Vis-NIR spectroscopy. Ab initio calculations reveal that small changes in the Ln3+ coordination spheres of these complexes can have relatively large influences on crystal field splitting.

Graphical abstract: Synthesis and characterisation of light lanthanide bis-phospholyl borohydride complexes

Supplementary files

Article information

Article type
Paper
Submitted
03 Apr 2020
Accepted
27 Apr 2020
First published
28 Apr 2020
This article is Open Access
Creative Commons BY license

Dalton Trans., 2020,49, 6504-6511

Synthesis and characterisation of light lanthanide bis-phospholyl borohydride complexes

J. Liu, L. E. Nodaraki, P. J. Cobb, M. J. Giansiracusa, F. Ortu, F. Tuna and D. P. Mills, Dalton Trans., 2020, 49, 6504 DOI: 10.1039/D0DT01241F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements