ISSN:
0044-2313
Keywords:
Aminoindene
;
cymantrene
;
zinc complex
;
crystal structure
;
manganese
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthesen und Kristallstrukturen von 2-Aminoindenen und AminocymantrenenSubstituierte 2-Aminoindene werden in nahezu quantitativer Ausbeute bei der Reaktion von Aminen wie Methylpiperazin, Trimethylethylendiamin, 1,4-Diazacycloheptan und N,N′-Dimethylethylendiamin mit 2-Indanon gebildet. Diese 2-Aminoindene können deprotoniert und mit BrMn(CO)3(py)2 in 55-70% Ausbeute zu den entsprechenden Aminoindenyl-Cymantren-Derivaten umgesetzt werden. Die Einkristallstrukturanalysen von 2-(Methylpiperazin)indenylcymantren 5 (P1, a = 12.667(3) Å, b = 16.630(3) Å, c = 17.382(3) Å, α = 72.70(3)°, β = 74.59(3)°, γ = 88.66(3)°, V = 3364.1(12) Å3, Z = 8, R1(2σ(I)) = 4.02%, wR2(2σ(I)) = 10.30%) und die HClO4-Adduktes von 2-(Trimethylethylendiamin)indenyl-cymantren 6 (Cc, a = 23.722(5) Å, b = 6.9080 Å, c = 13.264 Å, β = 111.77(3)°, V = 2018.6(7) Å3, Z = 4, R1(2σ(I)) = 2.94%, wR2(2σ(I)) = 7.90%) wurden bestimmt. In beiden Komplexen weist das am Indenyl-Stickstoff gebundene Kohlenstoffatom deutlich längere Bindungen zum Mangan auf [223.5(3) - 225.8(3) pm] als die vier anderen Kohlenstoffatome [213.3(3) - 219.1(3) pm]. Die kurzen Indenyl-Stickstoff-Abstände von 136.2(4) und 137.8(4) pm belegen den substantiellen Mehrfachbindungscharakter dieser Bindung. Die Komplexierung von Zn2+ durch die Stickstoffatome in 6 hat deutliche Verschiebungen der CO-Valenzschwingungen zur Folge.
Notes:
Substituted 2-aminoindenes have been synthesized in almost quantitative yields by reactions of amines such as methylpiperazine, trimethylethylenediamine, 1,4-diaza-cycloheptane and N,N′-dimethylethylenediamine with 2-indanone. The 2-aminoindenes can be deprotonated and reacted with BrMn(CO)3(Py)2 to produce the respective aminoindenyl-cymantrenes in yields between 55-70%. The X-ray crystal structures of 2-(methylpiperazine)indenyl-cymantrene 5 (P1, a = 12.667(3) Å, b = 16.630(3) Å, c = 17.382(3) Å, α = 72.70(3)°, β = 74.59(3)°, γ = 88.66(3)°, V = 3364.1(12) Å 3, Z = 8, R1(2σ(I)) = 4.02%, wR2(2σ(I)) = 10.30%) and the HClO4 adduct of 2-(trimethylethylenediamine)-indenyl-cymantrene 6 (Cc, a = 23.722(5) Å, b = 6.9080 Å, c = 13.264 Å, β = 111.77(3)°, V = 2018.6(7) Å 3, Z = 4, R1(2σ(I)) = 2.94%, wR2(2σ(I)) = 7.90%) were determined. In both complexes the indenyl-carbon bonded to nitrogen displays significantly longer bonds to manganese [223.5(3)-225.8(3) pm] than the other four carbon atoms [213.3(3)-219.1(3) pm]. The short indenyl-nitrogen bonds of 136.2(4) and 137.8(4) pm are indicative of a substantial multiple bond character. The complexation of Zn2+ by the nitrogen atoms of 6 results in significant shifts of the CO stretching frequencies.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19966220204
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