Intramolekular stabilisierte Übergangsmetallamide: 2‐(Dimethylaminomethyl)pyrrolyl‐Komplexe des Titan(III), Vanadium(III), Chrom(III), Cobalt(II) und Nickel(II)

Abstract

Intramolecularly Stabilized Metal Amides: 2-(Dimethylaminomethyl)pyrrolyl Complexes of Titanium(III), Vanadium(III), Chromium(III), Cobalt(I1) and Nickel(I1)By the metallation of 2-(dimethylaminomethy1)pyrrol (HL) of these new compounds are discussed on the basis of mawith butyllithium the lithium pyrrolide LiL (1) was obtained. gnetic and visible absorption measurements. An X-ray cry-

Co(II) Amide, Pyrrolate, and Aminopyridinate Complexes: Assessment of their Manifold Structural Chemistry and Thermal Properties

“…Drevs [19] and Holm [22] had originally described elaborate and time-consuming multistep synthesis procedures that we found to be avoidable by a direct transpyrrolylation approach employing 1 and the respective protonated pyrrole derivate in Et2O under mild refluxing conditions for several hours. This preparation method allowed to isolate the crude products nearly quantitatively with subsequent crystallization (8) or sublimation (9) giving the purified title compounds in yields of ~ 75 % -80 % as brown-red to red solids (Scheme 4).…”

“…This is likewise applicable to Co(II) pyrrolate and aminopyridinate complexes of which a few examples have been reported but never been compared in terms of structure and thermal properties. [18][19][20][21][22] Aiming to broaden the knowledge on selected Co(II) (silyl)amides and some of their Lewis adducts as well as Co(II) pyrrolates and aminopyridinates, this study provides a detailed survey over and comparison of the manifold structural chemistry of in total eleven complexes. First, utilizing the silylamide ligand 2,2,5,5-tetramethyl-1,2,5-azadisilolidinyl, a close structural relative to [Co(TMSA)2]2 is presented.…”

“…Furthermore, a straightforward and simplified protocol for the synthesis of two related Co(II) pyrrolates by transpyrrolylation of [Co(TMSA)2]2 is described. Hereby, the title compounds, chelated by the N,N'-2-(dimethylaminomethyl)pyrrolyl, [19] and N-2-(tertbutyliminomethyl)pyrrolyl [21] ligand, have been reported prior but not yet been compared in terms of structure and thermal properties. Sharing a chelating nature, the two amido-amino ligands N,N-dimethyl(N'-tert-butyl)ethane-1-amino-2-amide and N,N-dimethyl(N'trimethylsilyl)ethane-1-amino-2-amide are moreover employed to synthesize novel 4-fold coordinated Co(II) amide complexes with distorted tetrahedral geometry.…”

Synthesis, Structures and Characterization of the Calcium Pyrrolates [Ca{(2‐(dimethylaminomethyl)pyrrolyl}2 donorn] (donor = THF and pyridine, n = 2; DME and TMEDA, n = 1) as Potential Precursors for Solid‐State Applications

“…In fact, welcharacterized main group derivatives are limited to aluminum, [13] gallium and indium [14] in addition to some recently published mixed magnesium cyclopentadienide/amido derivatives. [15] Other metal complexes bearing DMAMP-type ligands include titanium, [16] tungsten, [16] zirconium, [17Ϫ19] vanadium, [19] thallium, [20] chromium, [19] molybdenum, [21] cobalt [19] and nickel. [19] Pyrrolylcalcium and -strontium derivatives with two tertbutyl substituents have been reported.…”

“…[15] Other metal complexes bearing DMAMP-type ligands include titanium, [16] tungsten, [16] zirconium, [17Ϫ19] vanadium, [19] thallium, [20] chromium, [19] molybdenum, [21] cobalt [19] and nickel. [19] Pyrrolylcalcium and -strontium derivatives with two tertbutyl substituents have been reported. [22] This sterically demanding ligand disfavors the η 1 -type bonding observed in the 2-DMAMP compounds; instead, π-bonding involving an η 5 arrangement is observed.…”