Protonation and Sulfidation of [(Me3tacn)MO3] (M=Mo, W). Issue 46 (8th December 2022)

• Record Type: Journal Article
• Authors: Cheng, Yao; Xu, Qian Y.; Qian, Bing F.; Zhang, Cai X.; Jia, Ai Q.; Zhang, Qian F.
• Is Part Of: ChemistrySelect. Volume 7:Issue 46(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-08
• Subjects: Molybdenum -- Tungsten -- 1, 4, 7-Trimethyl-1, 4, 7-triazacyclononane -- Protonation -- Sulfidation; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.202203785
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: Protonation of [(Me3 tacn)MoO3 ] with one or two equivalents of strong proton acid afforded mono‐protonated complex [(Me3 tacn)Mo VI O2 (OH)](CF3 SO3 ) and bi‐protonated complex [(Me3 tacn)Mo VI O(OH)2 ](PF6 )2, respectively. Sulfidation with i Pr2 NCS2 Na or CS2 in acetonitrile, followed by in situ protonation of [(Me3 tacn)MO3 ] (M=Mo, W), produced two monomeric complexes [(Me3 tacn)Mo VI O2 S] ⋅ ( i Pr2 NH2 ) ⋅ (PF6 ) ⋅ CH2 Cl2 and [(Me3 tacn)W VI O2 S], and two dimeric complexes [(Me3 tacn)Mo V O( μ ‐S)2 Mo V O( κ 2 ‐S2 C=O)] ⋅ CH3 CN and [(Me3 tacn)Mo IV O]2 ( μ ‐O)( μ ‐S2 ) ⋅ 2DMF. The crystal structures of the two protonated molybdenum(VI) complexes and the four oxo‐sulfido molybdenum/tungsten complexes have been determined. Moreover, the complexes have been characterized by infrared, Raman, fluorescence and UV‐vis spectroscopies. (Me3 tacn=1, 4, 7‐trimethyl‐1, 4, 7‐triazacyclonane). Abstract : Protonation with strong proton acid prior to the sulfidation of [(Me3 tacn)MO3 ] (M=Mo, W) was proposed and proved to be an efficient method for sulfidation of MO3 fragments.