Can bismuth replace mercury in redox transmetallation/protolysis syntheses from free lanthanoid metals?

Guo, Zhifang, Blair, Victoria, Deacon, Glen B., and Junk, Peter C. (2018) Can bismuth replace mercury in redox transmetallation/protolysis syntheses from free lanthanoid metals? Chemistry: a European journal, 24 (66). pp. 17464-17474.

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Tris(pentafluorophenyl)bismuth has been examined as a potential replacement for diarylmercurials in redox transmetallation/protolysis (RTP) syntheses of reactive rare earth compounds from free rare earth metals, HgAr2, and a proligand HL. Thus, the lanthanoid pyrazolates, [Ln(Ph2pz)3(thf)3] (Ph2pz=3,5‐diphenylpyrazolate; Ln=La, 1, Ce, 2, Nd, 3, Tb, 4; thf=tetrahydrofuran), [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (Ln=Ho, 5, Er, 6, Tm, 7, Lu, 8; dme=1,2‐dimethoxyethane), [Ln(Ph2pz)3(dme)2] (Ln=Dy, 9, Sm, 10), [Ln(tBu2pz)3(thf)2] (tBu2pz=3,5‐di‐tert‐butylpyrazolate; Ln=La, 11, Ce, 12, Sm, 13, Gd, 14, Dy, 15, Ho, 16, Tm, 17, Yb, 18, Lu, 19), [Ln(ttfpz)3(thf)3] (ttfpz=3‐(2′‐thienyl)‐5‐(trifluoromethyl)pyrazolate; Ln=La, 20, Sm, 21), and [Er(PhMepz)3(thf)2] 22 (PhMepz=3‐phenyl‐5‐methylpyrazolate) have been prepared in good yields by redox transmetallation/protolysis reactions employing lanthanoid metals and trispentafluorophenylbismuth [Bi(C6F5)3]⋅0.5 diox (diox=1, 4‐dioxane) in donor solvents. This is a new and efficient synthetic route in which Bi(C6F5)3 replaces the commonly used Hg(C6F5)2 or HgPh2, and provides proof of concept for the method. [Ln2(Ph2pz)4(OMe)2(dme)2]⋅2 dme (5–8) complexes are derived from C−O bond activation of dme on crystallization of the initial products from this solvent, and are dimeric methoxide‐bridged species. Other structures are monomeric with η2‐bound pyrazolate ligands and nine‐coordinate metal atoms for complexes 1–4, 9–10 and 20–21, and eight‐coordinate metal atoms for complexes 11–19 and 22.

Item ID: 56660
Item Type: Article (Research - C1)
ISSN: 1521-3765
Keywords: crystal structures, lanthanoid metals, lanthanoid pyrazolates, new synthetic method, redox transmetallation/protolysis (RTP) reactions, trispentafluorophenylbismuth (Bi(C6F5)(3))
Copyright Information: © 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
Funders: Australian Research Council (ARC)
Projects and Grants: ARC DP 160101640
Date Deposited: 19 Dec 2018 07:43
FoR Codes: 34 CHEMICAL SCIENCES > 3402 Inorganic chemistry > 340203 F-block chemistry @ 50%
34 CHEMICAL SCIENCES > 3402 Inorganic chemistry > 340205 Main group metal chemistry @ 50%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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