Heavier Chalcogenate‐Bridged Manganese Carbonyl Complexes: Synthesis, Reactivity, and Electrochemical Investigation
Year: 2025
Type: article
Abstract: The chemistry and electrochemical properties of heavier chalcogen‐supported (Se or Te) dimanganese complexes have been described. The photolytic reaction of [Mn 2 (CO) 10 ] with NaER [E = S, R = Ph; E = Se, R = Ph; E = Te, R = Ph; E = Se, R = ─C 6 H 4 ‐ p ‐NMe 2 ], followed by [( n ‐Bu) 4 NI] led to the formation of [( n ‐Bu) 4 N] + [(CO) 3 Mn( μ ‐ER) 3 Mn (CO) 3 ]¯ [E = S, R = Ph ( 1 ); E = Se, R = Ph ( 2 ); E = Te, R = Ph ( 3 ); E = Se, R = ─C 6 H 4 ‐ p ‐NMe 2 ( 4 )] complexes. Complexes 1 and 2 were employed for electrocatalytic hydrogen evolution in the presence of HBF 4 . The reported complexes were found to be catalytically inefficient. Complexes 1 – 4 showed quasi‐reversible oxidation peaks, and the reaction of 2 and 3 with dry oxygen resulted in the formation of dichalcogenides. This illustrates, in particular, how these complexes' oxygen tolerance differs owing to the chalcogen identity. The reaction of these trichalcogenate‐bridged dimanganese complexes 2 and 4 with HBF 4 , resulted in the formation of cubane‐type structure [(CO) 3 Mn( μ ‐SeR)] 4 [E = Se, R = Ph ( VII ); E = Se, R = ─C 6 H 4 ‐ p ‐NMe 2 ( 5 )]. The photolytic reaction of [Mn 2 (CO) 10 ] with NaER [E = Se, R = ─C 6 H 4 ‐ p ‐NMe 2 ], followed by (Cp*CoCl) 2 resulted in the formation of a heterobimetallic triselenolate‐bridged complex ( 6 ). These complexes were characterized by employing different multinuclear NMR, IR spectroscopies, single‐crystal X‐ray diffraction analyses, and mass spectrometry.
Source: Chemistry - An Asian Journal
Authors: Shivankan Mishra, Thinles Dolkar, Anvay Pareek, Roni Maji, Arnab Dutta, Sundargopal Ghosh
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: bronze
Awards: G3095123153, G5448675124, G876599304
OpenAlex ID: W4409647564