Related Experiment Video
Updated: Jun 10, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Sulfur-based redox reactions in Mo3S7(4+) and Mo3S4(4+) clusters bearing halide and 1,2-dithiolene ligands: a mass
Rosa Llusar1, Victor Polo, Ederley Velez
1Departament de Química Física i Analítica, Universitat Jaume I, Av. Sos Baynat s/n, 12071 Castelló, Spain.
Abstract:
The gas phase fragmentation reactions of sulfur-rich [Mo(3)S(7)Br(6)](2-) (1(2-)), [Mo(3)S(7)(bdt)(3)](2-) (2(2-)), and [Mo(3)S(4)(bdt)(3)](2-) (3(2-)) (bdt = benzenedithiolate) complexes have been investigated by electrospray ionization (ESI) tandem mass spectrometry and theoretical calculations at the density functional theory level. Upon collision induced dissociation (CID) conditions, the brominated 1(2-) dianion dissociates through two sequential steps that involves a heterolytic Mo-Br cleavage to give [Mo(3)S(7)Br(5)](-) plus Br(-) followed by a two-electron redox process that affords [Mo(3)S(5)Br(5)](-) and diatomic S(2) sulfur. Dianion [Mo(3)S(7)(bdt)(3)](2-) (2(2-)) dissociates through two sequential redox processes evolving diatomic S(2) sulfur and neutral bdt to yield [Mo(3)S(5)(bdt)(3)](2-) and [Mo(3)S(5)(bdt)(2)](2-), respectively. Conversely, dianion [Mo(3)S(4)(bdt)(3)](2-) (3(2-)), with sulfide instead of disulfide S(2)(2-) bridged ligands, remains intact under identical fragmentation conditions, thus highlighting the importance of disulfide ligands (S(2)(2-)) as electron reservoirs to trigger redox reactions. Regioselective incorporation of (34)S and Se at the equatorial position of the Mo(3)S(7) cluster core in 1(2-) and 2(2-) have been used to identify the product ions along the fragmentation pathways. Reaction mechanisms for the gas-phase dissociation pathways have been elucidated by means of B3LYP calculations, and a comparison with the solution reactivity of Mo(3)S(7) and Mo(3)S(4) clusters as well as closely related Mo/S/dithiolene systems is also discussed.
More Related Videos
08:50Preparation of Large-area Vertical 2D Crystal Hetero-structures Through the Sulfurization of Transition Metal Films for Device Fabrication
Published on: November 28, 2017
10:42Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Related Concept Videos
Preparation and Reactions of Sulfides
Preparation and Reactions of Thiols
Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Valence Bond Theory
Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
Structure and Nomenclature of Thiols and Sulfides