Identification of key reaction products from MoO[subscript 3] and ethylene glycol mixtures used for attempted MoS[subscript 2] electrodeposition and synthesis of bidentate ligands and related group 1 and 13 metal complexes

Abstract

Replication of a procedure to electrodeposit MoS₂ required use of an uncharacterized crude MoO₃ and ethylene glycol reaction mixture as a molybdenum precursor. Multiple attempts to replicate the desired &ldquo;brown oil&rdquo; resulted in isolating four crystals, with three being previously unknown products for this reaction. This evidence highlights possible identities for the molybdenum precursor responsible during this MoS₂ electrodeposition.<br /> A sterically bulky phosphine-imine treated with either H₂O₂, S₈, Se⁰ , or reacted with 9-bromofluorene followed by one equivalent of a base made four ligand precursors that can be deprotonated to act as mono-anionic ligands for a variety of metal complexes including Li-K, Al, and In. The four ligands undergo tautomerization revealing 2-4 isomers observed by ¹H, ¹³C, and ³¹P NMR spectroscopy, with two of these supported by SC-XRD analysis. Alkali metal complexes showed diverse &eta;² to &eta;⁴⁺⁶ interactions with the delocalized phosphonium fluorenylide and &eta;¹ /&eta;² with 2,6-diisopropylphenyl aromatic ring systems.