Abstract
A convenient pathway to new molecular organo-lanthanide-polyarsenides in general and to a f-element complex with the largest polyarsenide ligand in detail is reported. For this purpose, the activation of the solid state material As0nano (nanoscale gray arsenic) by the multi electron reducing agents [K(18-crown-6)][(Ln+II)2(μ-η6:η6-C6H6)] (Ln = La, Ce, Cp′′ = 1,3-bis(trimethylsilyl)cyclopentadienyl anion) and [K(18-crown-6)]2[(Ln+II)2(μ-η6:η6-C6H6)] (Ln = Ce, Nd) is shown. These non-classical divalent lanthanide compounds were used as three and four electron reducing agents where the product formation can be directed by variation of the applied reactant. The obtained Zintl anions As33−, As73−, and As144− were previously not accessible in molecular 4f-element chemistry. Additionally, the corresponding compounds with As144−-moieties represent the largest organo-lanthanide-polyarsenides known to date.
Highlights
Zintl anion and Zintl cluster chemistry is a traditional topic in inorganic chemistry.[1]
P4 tetrahedron to form butter y-type structures is known.[11,12,13,14,15]. While most of these reactions were reported with main group and transition metals, f-elements were less investigated and focused more on the lighter homologue nitrogen.[16,17,18,19]
The heavier molecular congener As4 is inconvenient to synthesise, highly prone to decompose into its thermodynamically stable modi cation and extremely photosensitive.[20]
Summary
Zintl anion and Zintl cluster chemistry is a traditional topic in inorganic chemistry.[1]. We report a new pathway towards organo-f-element arsenic Zintl ions beyond Sm by combining the solid-state material As0nano with the high redox potentials of various molecular non-classical divalent lanthanide compounds.
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