Electron-Rich Nitrido-Bridged Complexes. Structure and Bonding in Triosmium Dinitrido Compounds

Abstract

Triosmium dinitrido-bridged compounds Os3(N)2Cl8L6 (L = 3-picoline, 4-ethylpyridine, 4-tert-butylpyridine) have been prepared via the thermolysis of the terminal nitrido complexes Os(N)Cl3L2. X-ray structural studies of Os3(N)2Cl8(4-Etpy)6 and Os3(N)2Cl8(4-t-Bupy)6 reveal a linear Os3(N)2 unit with multiple bonding significantly localized in the outer osmium−nitrogen bonds in OsV⋮NOsIVN⋮OsV. A simple model of bonding and electronic structure consistent with the solid-state structures is discussed.

Early Transition‐Metal Hydrazido Complexes: Masked Metallanitrenes from NN Bond Scission

“…The terminal nitrogen group can therefore undergo a variety of transformations, such as oligomerization, [2] reductive coupling, [2,3] and N-addition reactions.…”

“…Applying the latter set of principles, the groups of Gade [7] and Mountford [8] have devised a strategy to trap metallanitrenes of zirconium(IV) and titanium(IV), respectively. Expounding on Walsh, Carney, and Bergmans seminal work on the reactivity of the transient zirconium(IV) hydrazido complex "[Cp 2 Zr=NNPh 2 ]" with CO to yield [Cp 2 Zr(NCO)(NPh 2 )] (Scheme 1), [9] Gade has devised a similar approach to trapping metallanitrenes with CNtBu, episulfides, and Ph 3 P = Se. As a result, the electrophilic zirconitrene motif, {Zr À N}, can form unusual functionalities, such as metallacarbodiimides by the coupling of the nitrene with CNtBu, as well as the assembly of dinitridosulfate(IV) and dinitridoselenate(IV) ligands onto zirconium(IV) by treating the hydrazido group with sulfide and selenide sources, respectively (Scheme 2).…”

Hydrazidokomplexe früher Übergangsmetalle: maskierte Metallanitrene durch Spaltung von N‐N‐Bindungen

“…[1] Als Folge kann die terminale Nitrid-Gruppierung aufgrund einer schwachen oder verbotenen Überlappung zwischen den Metall-und den Stickstofforbitalen auch zwischen radikalischen Resonanzstrukturen [M=NC $ MÀND] oder anderen kanonischen Formen wechseln, und der terminale Stickstoff kann somit vielfältige Umwandlungen wie Oligomerisierungen, [2] reduktive Kupplungen [2,3] und N-Additionsreaktionen eingehen.…”

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

“…Allg. Butylpyridin)[23]. 2000, 626, 1613±1619 Ó WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 0044±2313/00/6261613±1619 $ 17.50+.50/0 1613 Die Umsetzung von ReNCl 2 (PMe 2 Ph) 3 mit SbCl 5 in Toluol fu È hrt nicht zur Ausbildung einer Nitridobru È cke ReºN±Sb.…”