Functionalised alkaline earth iodides from Grignard synthons "PhAeI(thf)ₙ" (Ae = Mg‐Ba)

de Bruin-Dickason, Caspar N., Deacon, Glen B., Jones, Cameron, Junk, Peter C., and Wiecko, Michal (2019) Functionalised alkaline earth iodides from Grignard synthons "PhAeI(thf)ₙ" (Ae = Mg‐Ba). European Journal of Inorganic Chemistry, 2019 (7). pp. 1030-1038.

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Abstract

Derivatisation of Grignard synthons "PhAeI(thf)(n)" (Ae = Mg-Ba) prepared in situ from reactions of metal filings and iodobenzene provides a one-pot synthesis of heteroleptic N donor alkaline earth iodide complexes. Protolysis of "PhAeI(thf)(n)" with 3,5-diphenylpyrazole (Ph(2)pzH) yields pyrazolate complexes [Mg-2(mu-Ph(2)pz)(2)(I)(2)(thf)(3)] (1), [Ae(Ph(2)pz)(I)(thf)(4)] (Ae = Ca (2), Sr (3)), and [Ba-2(Ph(2)pz)(2)(mu-I)(2)(thf)(8)] (4). Addition of the Ae-Ph moiety to carbodiimide MesN=C=NMes (Mes = 2,4,6-(CH3)(3)C6H2) gave a series of benzamidinate iodide complexes [Ca-2{(MesN)(2)CPh}(2)(mu-I)(2)(thf)(4)] (6), [Sr{(MesN)(2)CPh}(I)(thf)(4)] (7), and [{Ba{(MesN)(2)CPh}(mu-I)(thf)(3)}(infinity)] (8). By contrast a symmetrical magnesium complex [Mg{(MesN)(2)CPh}(2)(thf)] (5) was obtained by Schlenk redistribution. These syntheses proceed without pre-activation of the metal for strontium and barium, and after activation with 2 mol-% iodine for calcium. The heavy alkaline earth metal complexes are the first examples of heteroleptic halide pyrazolate or amidinate complexes for strontium and barium. Complexes 1, 3, 4 and 6-8 were characterised crystallographically, revealing diverse structural chemistry of heteroleptic amidinate and pyrazolate iodide complexes across the alkaline earth series. A highlight is [Ba{(MesN)(2)CPh}(mu-I)(thf)(3)](infinity) (8) - an iodide bridged infinite 1-D polymer.

Item ID: 57431
Item Type: Article (Research - C1)
ISSN: 1099-0682
Keywords: alkaline earth metals, heavy Grignard chemistry, N ligands, structure elucidation
Copyright Information: © 2019 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
Funders: Australian Research Council (ARC), U.S. Air Force Asian Office of Aerospace Research and Development
Projects and Grants: ARC Discovery Grant DP160101640, U.S. Air Force Asian Office of Aerospace Research and Development grant FA2386‐18‐1‐0125
Date Deposited: 13 Mar 2019 07:53
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030204 Main Group Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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