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Chemistry of oxidomolybdenum(IV) and -(VI) complexes with ONS donor ligands: synthesis, computational evaluation and oxo-transfer reactions

Saswati, [no name] and Dash, Subhashree P. and Acharyya, Rama and Kaminsky, Werner and Ugone, Valeria and Garribba, Eugenio and Harris, Cragin and Lowe, Jared M. and Dinda, Rupam (2018) Chemistry of oxidomolybdenum(IV) and -(VI) complexes with ONS donor ligands: synthesis, computational evaluation and oxo-transfer reactions. Polyhedron, Vol. 141 , p. 322-336. ISSN 0277-5387. Article.

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DOI: 10.1016/j.poly.2017.12.023

Abstract

A series of dioxidomolybdenum(VI) complexes, [MoVIO2L1–6] (1–6) and [MoVIO2L1–6(solv)] (1a–6a) {where solv (solvent) = DMSO (1a, 3a, 5a and 6a) and H2O (2a and 4a)} have been synthesized using thiosemicarbazone ligands, H2L1–6. Furthermore, six monooxidomolybdenum(IV) complexes [MoIVOL1–6(N-N)] (7–12) {where co-ligand (N-N) = 2,2′-bipyridine (bipy) (7, 10 and 11) and 1,10-phenanthroline (phen) (8, 9 and 12)} have also been synthesized from the corresponding Mo(VI) precursors, [MoVIO2L1–6] (1–6) by oxygen atom transfer (OAT) reaction. Complexes have been characterized by conventional methods, including X-ray crystallography, and DFT (density functional theory) calculations. OAT reactivity of Mo(VI) and Mo(IV) complexes have been successfully established through the formation of OPPh3 and Me2S. These OAT products have been characterized by 31P NMR (OPPh3), UV–Vis spectroscopy and GC–MS (Me2S) and DFT simulations supported this finding through the prediction of ΔGtotsol for the reaction of oxygen atom transfer. DFT methods suggested that the oxygen atom transfer from [MoVIO2L] species to PPh3 to give [MoIVOL(bipy)] and from DMSO to [MoIVOL(bipy)] to yield [MoVIO2L] is strongly favored, whereas the formation of μ-oxido dimer [MoV2O3L2], is much less probable.

Item Type:Article
ID Code:11926
Status:Published
Refereed:Yes
Uncontrolled Keywords:Thiosemicarbazone, oxidomolybdenum(IV/VI), X-ray structure, OAT reaction, DFT studies
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01-a Nuovi Dipartimenti dal 2012 > Chimica e Farmacia
Publisher:Pergamon / Elsevier
ISSN:0277-5387
Deposited On:07 Feb 2018 10:44

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