Synthesis of Mn(III)X 3 (X = Cl, Br, I) Compounds with Phosphine (R 3 P) Ligands

This work details the synthesis and characterization of complexes of the form [Mn X (PR ) ] (X = Cl, Br, I), which is a rare type of coordination compound. Prior to this work, the only mode of synthesis was oxidizing mixtures of Mn X and PR with dry air, but these procedures give low yields and vari...

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Published in:Inorganic chemistry 2024-08, Vol.63 (34), p.15791-15803
Main Authors: Paul, Sanchita, Saju, Ananya, Cohen, Cooper, Crawley, Matthew R, MacMillan, Samantha N, Lacy, David C
Format: Article
Language:English
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Summary:This work details the synthesis and characterization of complexes of the form [Mn X (PR ) ] (X = Cl, Br, I), which is a rare type of coordination compound. Prior to this work, the only mode of synthesis was oxidizing mixtures of Mn X and PR with dry air, but these procedures give low yields and variable outcomes. By taking advantage of the starting material [Mn Cl (OPPh ) ] ( ) and other new strategies, we present robust synthetic protocols for both new and known Mn(III) halido phosphine complexes. In addition to [Mn X (PR ) ], these include [Mn Cl (dmpe) ] salts and [LMn X ] manganates (L = phosphine oxide). Furthermore, the full characterization of these [Mn X (PR ) ] species enabled a definitive revisitation of some controversial chemistry surrounding the compounds and products from the dry air oxidation of certain Mn X and phosphine ligand mixtures.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.4c01820