Iron And Ruthenium Complexes With 1,2-Diaza-4-phospholide And Nitride Ligands

The five-membered heterocyclic 1,2-diaza-4-phospholides[3,5-R₂dp]^-(R=t Bu,thienyl)containing N and P atoms are expected to coordinate with metal ions through both N and P sites and thus afford the corresponding 1,2-diaza-4-phospholide complexes with varied coordination modes.1.In this contribution,the reaction of potassium 1,2-diaza-4-phospholide K[3,5-R₂dp] (R=t Bu)and[(?⁶-p-cymene)Ru Cl]₄ was carried out to afford a ruthenium 1,2-diaza-4-phospholidecomplex [(?⁶-p-cymene)Ru{?¹(N),?¹(P)-?¹(C)-3-t Bu-5-CMe₂(CH₂)dp]₄(1)in which an unusual C(sp³)-H activation occurred.The tetranuclear 1,2-diaza-4-phosphine ruthenium(II)[(?⁶-p-cymene)Ru{?¹(N),?¹(P)-?¹(C)-3-t Bu-5-CMe₂(CH₂)dp]₄(1) was isolated with unexpected C(sp³)–Ru and P(?²?³)-Ru?-bonds.The formation of C(sp³)–Ru?-bonds arises from a selectively ruthenium(II)C(sp³)–H activation between Ru(II)and C-H bond of 1,2-diaza-4-phospholide that plays a double role in providing both the site for methyl metalation and acting as a base;2.Organoruthenium azides[Ru]-N=N=N([Ru]=metal organic molecule)are expected to react with unsaturated organic compounds containing triple bonds such as CoN-R via a[3+2]cycloaddition to generate the corresponding [Ru]-five-membered heterocyclic intermediates that could be easily transferred to the related organic compounds.The reaction of[Cp Me₅Ru Cl(Pi Pr₃)]and sodium azide was thus carried out to give an unusual organoruthenium azide [?⁵-Cp Me₅Ru(?₂-i Pr₃PN₃)]₂(2).3.The reaction of potassium 1,2-diaza-4-phospholide K[3,5-R₂dp](R=thienyl)and [Cp Me₅FeCl]gavea1,2-diaza-4-phospholideferrocene[?⁵-Cp Me₅Fe(?⁵-3,5-thieny₂dp)](3).Compounds 1-3 were characterized by X-ray single crystal structure analysis,nuclear magnetic resonance spectroscopy(NMR),infrared spectroscopy(IR),UV-spectroscopy(UV),and cyclic voltammetry(CV).