Stepwise construction and destruction of nickel thiolate Ni-3 cluster revealed by mass spectrometry and crystallography

摘要

Trinuclear nickel thiolate cluster [Ni-3(mu(3)-S)(L)(3)]NO3 (HL = (1-methyl-1H-benzo[d]imidazol-2-yl)methanethiol) (1) has been synthesized from Ni(NO3)(2)center dot 6H(2)O and HL at solvothermal condition at 80 degrees C using methanol as solvent. It has been characterized by X-ray single crystal diffraction, elemental analysis, electrospray ionization mass spectrometry (ESI-MS), and thermogravimetric analysis. The stability of the cluster in methanol is reflected by the fact that the molecular ion peak of [Ni-3(mu(3)-S)(mbms)(3)](+) is dominant in ESI-MS. Furthermore, the release of H2S from 1 was observed at elevated in source energy condition and in tandem mass spectrometry. The H2S fragment was also detected during the destruction of 1 by thermogravimetric analysis combined with mass spectrometry (TG-MS). Key fragments [NiLS] and [Ni2L2](+) were percepted in solution by ESI-MS during the reaction, which have also been detected at elevated in source energy condition. A plausible stepwise assembly process including [NiL](+) to the mixture of [NiLS](+) and [Ni2L2](+) which then combined to give the product [Ni3L3S](+) was proposed.