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  • 1
    ISSN: 0044-2313
    Keywords: Copper(I) ; 1-azadienes ; oxidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Copper(I) Complexes with 1-Azadiene Chelate Ligands and Their Reaction with OxygenThe reaction of the bidendate 1-azadiene ligands Me2N—(CH2)n—N=CH—CH=CH—Ph with CuX results in the formation of the dimeric compounds [ACuX]2 and [BCuX]2 (A: n = 2, B: n = 3, X: I, Cl). The structure of complex 1 [ACuI]2 was determined by X-ray crystal structure analysis. 1 consists of two tetrahedrally coordinated Cu atoms connected by two iodo bridges. (Cu—Cu bond length: 261 pm).The ligand Me—N(CH2CH2N=CH—CH=CH—Ph)2 (C) reacts with CuX to form the monomeric complexes [CCuX] (5: X=I, 6: X=Cl). The crystal structure of 5 shows that the ligand acts as a tridendate ligand. The bond lengths of the CuN(sp2) bonds are significantly shorter than the Cu—N(sp3) distance.Reacting the podand-type ligands N(CH2CH2—N=CH—R)3 (D: R=Ph, E: R=-CH=CH—Ph) with CuX yields the ionic complexes 7 [DCu][CuCl2] and 8 [ECu][CuCl2]. 7 was characterized by X-ray analysis which confirmed that D acts as a four-dendate podand ligand.The compounds 1-8 are unreactive towards CO2 but take up O2 even at deep temperatures. At -78°C the orange-red complex 4 [BCuCl]2 reacts with O2 in CH2Cl2 to form a deep violet solution, but the primary product of the oxidation could not be isolated. It reacts at room temperature to form the green complex 9 [μ-Cl, μ-OH][BCuCl]2. The X-ray structure analysis of 9 confirms that a dimeric CuII complex is formed in which both a chloro- and a hydroxo group are bridging the monomeric units. The CuII centers exhibit a distorted tetragonal-pyramidal coordination.The pathway of the reaction with O2 will be discussed.
    Notes: Die Reaktion der zweizähligen 1-Azadienliganden Me2N—(CH2)n—N=CH—CH=CH—Ph mit CuX führt zu den dimeren Komplexen [ACuX]2 and [BCuX]2 (A: n = 2, B: n = 3, X: I, Cl). Die Struktur des Komplexes 1 [ACuI]2 wurde durch Kristallstrukturanalyse bestimmt. 1 enthält zwei tetraedrisch koordinierte Cu-Atome, die über zwei Iodobrücken miteinander verknüpft sind Cu—Cu-Bindungslänge: (261 pm).Der Ligand Me—N(CH2CH2N=CH—CH=CH—Ph)2 (C) reagiert mit CuX unter Bildung der monomeren Komplexe [CCuX] (5: X = I, 6: X=Cl). Die Kristallstruktur von 5 zeigt, daß der Ligand dreizählig koordiniert. Die Bindungslängen der Cu—N(sp2)-Bindungen sind signifikant kleiner als der Cu—N-(sp3)-Abstand.Die Reaktion der Podand-Liganden N(CH2CH2—N=CH—R)3 (D: R=Ph, E: R=-CH=CH—Ph) mit CuX führt zu den ionischen Komplexen 7 [DCu][CuCl2] bzw. 8 [ECu][CuCl2]. 7 wurde durch Röntgenstrukturanalyse charakterisiert, die ausweist, daß D als vierzähliger Ligand fungiert.Die Komplexe 1-8 sind gegenüber CO2 nicht reaktiv, nehmen aber O2 schon bei tiefen Temperaturen auf. Bei -78°C reagiert der orangerote Komplex 4 [BCuCl]2 mit O2 in CH2Cl2 zu einer tiefvioletten Lösung, das Primärprodukt der Oxidation konnte jedoch nicht isoliert werden. Es reagiert bei Raumtemperatur zu dem grünen Komplex 9 [μ-Cl, μ-OH][BCuCl]2. Die Kristallstrukturanalyse belegt, daß ein dimerer CuII-Komplex gebildet wird, in dem eine Chloro- und eine Hydroxobrücke die Monomereinheiten verbrücken. Die CuII-Zentren weisen eine verzerrt tetragonal-pyramidale Koordination auf.Der Reaktionsweg der Umsetzung mit O2 wird diskutiert.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Carbon dioxide fixation ; 1-Azadiene ligands ; Nickel(0) complexes ; Carboxylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organometallic CO2 Reservoires from Nickel(0)-1-Azadiene-Type Ligands and Their Reactivity in the Carboxylation of Acetophenone1-Azadiene-type ligands yield with nickel(0) binuclear organometallic compounds of the type [Ni(1-azadiene)n,]2 (n = 1, 2). The structures of the complexes 1 (n = 2, ligand A) and 3 (n = 1, ligand C) have been characterized by X-ray crystallography. 1 is unreactive towards CO2, 3 and similar compounds are able to react with CO2 to give metallacyclic carbamato complexes of Ni(II). In these compounds CO2 is activated and can carboxylate acetophenone to yield benzoylic acid upon protolysis. These reactions mimic biologic conversion reactions of CO2 into organic material by organometallics. - The addition of two moles of the (bpy)Ni(0)-fragment [from (bpy)Ni(COD)] to 3 gives the tetranuclear complex 6. The X-ray analysis of the monomeric model compound (bi-py)Ni(A) (11) shows that only the olefin part is coordinated. 6 and 11 can also react with CO2. Cu(I) complexes with 1-azadiene-type ligands are not reactive towards CO2.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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