Azidoruthenium(III) complexes as precursors for molecular nitrogen and nitrene complexes

Abstract

Corresponding to the intense (e 5000-12,000), structured charge-transfer band in the visible region (Table II) are found several distinct CD bands, interpreted, following Bosnich,3 as originating in transitions from d orbitals to the azomethine tt* (a2, bx, in the coordinate scheme of Belford19) orbitals. For the benzenoid complexes, a consistent assignment of these bands can be proposed. Bands IV and V (see Table III), whose signs are positive and negative, respectively, in the complexes derived from (-)pn, and the opposite in the (-)chxn

Formation of a Methyleneimine Moiety by Reaction of a RuII‐Coordinated Azide Ion with Methyl Iodide

“…The reaction proceeds via a reactive intermediate such as a nitrene and nitride complex, and N 2 is generated 1–5. Although azide compounds are explosive as a result of rapid dinitrogen evolution, azido–metal complexes can potentially to be converted into various nitrogen‐containing complexes such as imido and cycloaddition compounds 2–6. Di(azido)bis(2,2′‐bipyridine) complexes of Ru II and Ru III have been synthesized1, 7 and investigated in thermal and photochemical reactions 1.…”

Terminal Nitrido and Imido Complexes of the Late Transition Metals

“…[172] Ruthenium imido=nitrene complexes with structure types V or VI have also been proposed in several instances but not isolated. [173][174][175][176][177][178] Osmium imido species with structure V have been prepared from the corresponding Os(VI)-nitrido species; an example with Os in each of the three oxidation states Os(IV), Os(V), and Os(VI) is known. The Os(IV) complex, [(tpy)(bpy)Os=NÀNEt 2 ] 2+ , has been characterized by X-ray crystallography.…”

Synthesis and Reactivity of a Transient, Terminal Nitrido Complex of Rhodium

“…As was shown for analogous Ir nitride 3, the transient rhodium nitride 7 readily reacts via radical-type N−N coupling to the corresponding dimeric rhodium(I) N 2 complex 8. This mechanistic pathway might similarly apply to d 3 nitrides, such as iron(V) nitride 4 (Chart 1), 19 Full preparative, analytical, crystallographic, and computational details in pdf format. This material is free of charge via the Internet at http://pubs.acs.org.…”