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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1135-1143 
    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.
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  • 2
    ISSN: 0009-2940
    Keywords: Nickel(0) ; Alkyne complexes ; Hydrogen bonds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of (cdt)Ni (cdt: cyclododeca-1,5,9-triene) with 2 equivalents of 2-methyl-4-trimethylsilyl-3-butyn-2-ol leads to the selective formation of the homoleptic complex (alkyne)4Ni3 (compound 3), which can be isolated in excellent yields. The solid-state structure of 3 exhibits three Ni centers, forming a bent Ni3 chain connected by two bridging alkynes. The other two alkynes are terminally coordinated. Additionally, the trimeric units are stabilized by three intramolecular hydrogen bonds. Two intermolecular hydrogen bonds connect the trimeric units to form a polymer rope. According to the 13C- and 1H-NMR spectra in THF the structure of the complex 3 in solution is very similar to that in the solid state. The reaction of 3 with some alkynediols and with 2,5,5-trimethylhex-3-yn-2-ol affords compounds of the type (alkyne)2Ni. Cot (cot: 1,3,5,7-cyclooctatetraene) converts 3 into [(cot)Ni]2, which in turn reacts with 2,5-dimethylhex-3-yne-2,5-diol to form the dimeric complex (alkyne)2Ni2(cot) 6. X-ray analysis of 6 reveals a very symmetrical structure in which cot connects both Ni(0) centers at opposite sides of the ring system.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0044-2313
    Keywords: Nickel(0) ; binuclear compounds ; functionalized alkynes ; supramolecular structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Binuclear Nickel(0) Alkyne Coordination Compounds - Correlation between Ligand Periphery and Supramolecular StructureReaction of Ni(cdt: 1,5,9-cyclododecatriene) with functionalized alkynes and subsequent reaction with ethylenediamines gives binuclear compounds of the type (diamine)Ni(μ-alkyne)Ni(alkyne). Compounds with alkyne-diols (N⁁N)Ni2(HOR1R2C—C≡C—CR1R2OH)2 show supramolecular structures in which two identical intramolecular and one intermolecular hydrogen bonds are realized. 1 and 2 (chelate ligand in each case N,N,N′,N′-tetramethylethylenediamine, TMEDA, in 1 R1 = R2 = Me, in 2 R1 = R2 = Et) polymer-like chains are built up by connecting the binuclear units. Via two intermolecular hydrogen bonds per organometallic unit in 1 and via one intermoleculare hydrogen bond in 2 the chains are connected to give double chains. By substitution of one methyl group of TMEDA by hydrogen (3: R1 = R2 = Me) a polymerlike network is produced by connecting the polymer-like chains.In compound 4 in which one of the methyl groups of TMEDA is substituted by CH2CH2NMe2 the polymer-like chains remain unconnected. In 5 (diamine = TMEDA, alkyne = (CH3)3C—C≡C—CMe2OH) one intermolecular hydrogen bond per organometallic unit is observed forming again polymer-like chains that are independent of each other.
    Notes: Durch Reaktion von Ni(cdt) (cdt: Cyclododeca-1,5,9-trien) mit funktionalisierten Alkinen und anschließender Umsetzung mit Ethylendiaminen erhält man binucleare Alkin-Nickel(0)-Verbindungen des Typs (diamin)Ni(μ-alkin)Ni(alkin). In Verbindungen mit Alkindiolen (N ⁁ N)Ni2(HOR1R2C—C≡C—CR1R2OH)2 werden supramolekulare Strukturen aufgebaut, die jeweils zwei gleichartige intramolekulare und eine intermolekulare Wasserstoffbrückenbindung aufweisen. In 1 und 2 (Chelatligand jeweils N,N,N′,N′-Tetramethylethylendiamin, TMEDA, in 1 R1 = R2 = Me, in 2 R1 = R2 = Et) bilden sich durch Verknüpfung der binuklearen Einheiten polymere Stränge, die in 1 durch zwei und in 2 durch eine Wasserstoffbrückenbindung pro Organometalleinheit zu Doppelsträngen verknüpft werden. Ersatz einer Methylgruppe in TMEDA durch Wasserstoff (3: R1 = R2 = Me) bewirkt, daß die polymeren Stränge zu einem polymeren Netzwerk verknüpft werden. In Verbindung 4 (R1 = R2 = Me), in der im TMEDA eine Methylgruppe durch CH2CH2NMe2 ersetzt ist, bleiben die zu 1-3 analogen polymeren Stränge untereinander unverknüpft.In 5 (Diamin = TMEDA, Alkin = (CH3)3C—C≡C—CMe2OH) wird pro Organometalleinheit eine intermolekulare Wasserstoffbrückenbindung gebildet, was ebenfalls zu voneinander unabhängigen polymeren Strängen führt.
    Additional Material: 12 Ill.
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