Organometallic derivatives of Rh- and Ir-substituted polyoxotungstates with Keggin structure: reactivity screening by electrospray ionization mass-spectrometry

ESI-MS based methodology for the rapid reactivity screening of [PW11O39RhCl]5− and [PW11O39Ir(H2O)]4− toward various metalation-intended substrates (reagents with an activated C–H bond, boronic acids and organotin compounds) is presented. Formation of a series of new organometallic POM derivatives with Rh–R (R = malonate, phenylacetate, CH3, Ph, ferrocenyl) and Ir–R (R = CH3) bonds is reported

Cd²⁺ Complexation with P(CH₂OH)₃, OP(CH₂OH)₃, and (HOCH₂)₂PO₂^–: Coordination in Solution and Coordination Polymers

The coordination of Cd²⁺ with P­(CH₂OH)₃ (THP) in methanol was followed by ³¹P and ¹¹¹Cd NMR techniques. A cadmium-to-phosphine coordination ratio of 1:3 has been established, and effective kinetic parameters have been calculated. Air oxidation of THP in the presence of CdCl₂ at room temperature produces coordination polymer ³_∞[Cd₃Cl₆(OP­(CH₂OH)₃)₂] (<b>1</b>). The same oxidation reaction at 70 °C gives another coordination polymer, _∞[CdCl₂(OP­(CH₂OH)₃)] (<b>2</b>). Complexes <b>1</b> and <b>2</b> are the first structurally characterized complexes featuring OP­(CH₂OH)₃ as a ligand that acts as a linker between Cd atoms. The addition of NaBPh₄ to the reaction mixture gives coordination polymer _∞[Na₂CdCl₂(O₂P­(CH₂OH)₂)₂(H₂O)₃] (<b>3</b>) with (HOCH₂)₂PO₂^– as the ligand. Coordination polymers <b>1</b>–<b>3</b> have been characterized by X-ray analysis, elemental analysis, and IR spectroscopy

New {RuNO} Polyoxometalate [PW11O39RuII(NO)]4-: Synthesis and Reactivity

New Ru-containing polyoxometalate [PW11O39RuII(NO)]4- (14-) was obtained in high yield by reaction of [Ru(NO)Cl5]2- with [PW11O39]7- and characterized by multinuclear NMR, cyclic voltammetry, IR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS). The intrinsic reactivity of the {RuNO} site in 14- toward various reagents has been studied using a versatile and simple ESI tandem mass spectrometric methodology for identification of the L attached at the Ru site; this approach relies on the preferential liberation of the L ligands attached at the Ru sites upon mass-selecting desired intermediates and subsequent promotion of their fragmentation. Reactions with both hydrazine and hydroxylamine lead to elimination of the nitroso group and quantitative formation of [PW11O39RuIII(H2O)]4- (24-) in aqueous solution. In the reaction with hydroxylamine, an intermediate with coordinated dinitrogen has been detected. An easy access to the NH3-coordinated [PW11O39RuNH3]4- (34-) complex was achieved upon reduction of 14- with Sn2+ in water

New {RuNO} Polyoxometalate [PW₁₁O₃₉Ru^II(NO)]^4‑: Synthesis and Reactivity

New Ru-containing polyoxometalate [PW₁₁O₃₉Ru^II(NO)]^4‑ (<b>1</b>^4‑) was obtained in high yield by reaction of [Ru­(NO)­Cl₅]^2‑ with [PW₁₁O₃₉]^7‑ and characterized by multinuclear NMR, cyclic voltammetry, IR spectroscopy, and electrospray ionization mass spectrometry (ESI-MS). The intrinsic reactivity of the {RuNO} site in <b>1</b>^4‑ toward various reagents has been studied using a versatile and simple ESI tandem mass spectrometric methodology for identification of the L attached at the Ru site; this approach relies on the preferential liberation of the L ligands attached at the Ru sites upon mass-selecting desired intermediates and subsequent promotion of their fragmentation. Reactions with both hydrazine and hydroxylamine lead to elimination of the nitroso group and quantitative formation of [PW₁₁O₃₉Ru^III(H₂O)]^4‑ (<b>2</b>^4‑) in aqueous solution. In the reaction with hydroxylamine, an intermediate with coordinated dinitrogen has been detected. An easy access to the NH₃-coordinated [PW₁₁O₃₉RuNH₃]^4‑ (<b>3</b>^4‑) complex was achieved upon reduction of <b>1</b>^4‑ with Sn²⁺ in water