Synthesis of Silyl Iron Dinitrogen Complexes for Activation of Dihydrogen and Catalytic Silylation of Dinitrogen

Three novel iron dinitrogen hydrides, [FeH(iPr-PSiMeP)(N2)(PMe3)] (1), [FeH(iPr-PSiPhP)(N2)(PMe3)] (2), and [FeH(iPr-PSiPh)(N2)(PMe3)] (3), supported by silyl ligand are synthesized for the first time by changing the electronic effect and steric hindrance...

Silylamido supported dinitrogen heterobimetallic complexes: Syntheses and their catalytic ability

Molybdenum dinitrogen complexes supported by monodentate arylsilylamido ligand, [Ar(Me3Si)N]3MoN2Mg(THF)2[N(SiMe3)Ar] (5) and [Ar(Me3Si)N]3MoN2SiMe3 (6) (Ar = 3,5-Me2C6H3) were synthesized and structurally characterized, which were proved to be effective catalysts for the disproportionation of cyclohexadienes and isomerization of terminal alkenes. 1H NMR spectrum suggested that the bridging nitrogen ligand remains intact during the catalytic reaction, indicating the possible catalytic ability of Mo-N = N motif.

Trichloro(Dinitrogen)platinate(II)

<p>Zeise’s salt, [PtCl₃(H₂C=CH₂)]^–_, is the oldest known organometallic complex, featuring ethylene strongly bound to a platinum salt. Many derivatives are known, but none involving dinitrogen, and indeed dinitrogen complexes are unknown for both platinum and palladium. Electrospray ionization mass spectrometry of K₂[PtCl₄] solutions generate strong ions corresponding to [PtCl₃(N₂)]^–, whose identity was confirmed through ion mobility spectroscopy and MS/MS experiments that proved it to be distinct from its isobaric counterparts [PtCl₃(C₂H₄)]^– and [PtCl₃(CO)]^–. Computational analysis established a gas-phase platinum-dinitrogen bond strength of 116 kJ mol^-1, substantially weaker than the ethylene and carbon monoxide analogues but stronger than for polar solvents such as water, methanol and dimethylformamide, and strong enough that the calculated N-N bond length of 1.119 Å represents weakening to a degree typical of isolated dinitrogen complexes. </p>

Trichloro(Dinitrogen)platinate(II)

<p>Zeise’s salt, [PtCl₃(H₂C=CH₂)]^–_, is the oldest known organometallic complex, featuring ethylene strongly bound to a platinum salt. Many derivatives are known, but none involving dinitrogen, and indeed dinitrogen complexes are unknown for both platinum and palladium. Electrospray ionization mass spectrometry of K₂[PtCl₄] solutions generate strong ions corresponding to [PtCl₃(N₂)]^–, whose identity was confirmed through ion mobility spectroscopy and MS/MS experiments that proved it to be distinct from its isobaric counterparts [PtCl₃(C₂H₄)]^– and [PtCl₃(CO)]^–. Computational analysis established a gas-phase platinum-dinitrogen bond strength of 116 kJ mol^-1, substantially weaker than the ethylene and carbon monoxide analogues but stronger than for polar solvents such as water, methanol and dimethylformamide, and strong enough that the calculated N-N bond length of 1.119 Å represents weakening to a degree typical of isolated dinitrogen complexes. </p>