Kupfer(I)‐diazabutadien‐halogenide

Abstract

1.4-Diaza-butadiene-( 1.3) bilden mit Kupfer(1)-halogeniden stark farbige, monomere 1 : I -Komplexe 2 -11, 16-20, 24, 25 mit dreifach koordiniertem Kupfer. Diese Koordination bestimmt das elektronenspektroskopische Verhalten. Wahrend in Diazabutadien-Komplexen anderer Metalle in niedrigen Oxydationsstufen die Iangstwellige Absorption sehr starken Metall-Ligand-charge-transfer-Charakter hat, fehlt hier bei etwa gleich starker Beteiligung von Metalltermen im Grundzustand und angeregten Zustand die typische Soivatochromie und die extrem hohe Intensitat des farbgebenden Ubergangs. Copper(1)-diazabutadiene Halides1,4-Diazabuta-l,3-dienes react with cuprous halides to form strongly coloured, monomeric 1 :I adducts 2-11, 16 -20, 24, 25, containing copper with threefold coordination. This coordination number determines the spectroscopic behaviour. While diazabutadiene complexes of other metals in low oxidation states show a long-wavelength absorption with strong metalto-ligand CT character, in the copper complexes 2-11, 16--20, 24, 25 the metal terms are about equdlly important in the ground and excited state without showing the typical solvatochromism and the extremely high intensity of the chromogenic transition.

Photochemistry of the metal-metal-bonded complexes [(CO)5MnRu(Me)(CO)2(α-diimine)]. Crystal structure of the photoproduct [(CO)4Mn-μ-(σ(N),σ(N′),ν2(CN)-iPr-PyCa)Ru(Me)(CO)2]

“…The large nitrogen coupling constants observed for both radicals indicate that the unpaired electron is mainly localized on the a-diimine ligand. A similar conclusion was derived from the ESR spectra of the radicals [Mn(CO)3(tBu-DAB)] ", [Re(CO)3(a-diimine)]" and [Cr(CO)n(a-diimine)]- [6,33,34]. As indicated by the values of aRu and a N, this localization increases on going from the 1Pr-PyCa to the ipr-DAB radical complex.…”

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

“…Propadiene was purchased from Air Products, while 1,2-heptadiene, 34 (cis,cis-1,5-cyclooctadiene)Pd(Me)Cl, 35 [Pd(η 3 - 39 1,4-di-i-Pr-1,4-diaza-1,3-butadiene, 40 and 1,4-di-p-An-1,4-diaza-1,3-butadiene 40 were synthesized according to previously reported procedures.…”

Binuclear metal carbonyl R-DAB complexes. Part XIII. Reduction of coordinated 1,4-diaza-1,3-butadiene to dianionic 1,2-diaminoethane by [HFe(CO)4]−. Molecular structure of [(μ-H)FeMn(CO)6{μ,μ′-N(p-Tol)CH2CH2N(p-Tol)}], a pseudo-symmetrical hetero-dinuclear species

“…UV spectroscopic and electrochemical measurements have shown that the LUMO of aryl-DAB's is situated at lower energy than that of alkyl-DAB's, resulting in a greater reduction ability for the former [7]. In this paper we report the results of this study, showing that the reaction of [MnBr-…”