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Aryl‐(4‐arylimino‐4H‐pyrido[1,2‐a]pyrazin‐3‐yl)amine–Synthese, Komplexbildung mit Molybdän(0) und Oxigenierung

 

作者: Manfred Döring,   Egon Uhlig,   Jörg Wuckelt,   Rainer Beckert,   Helmar Görls,   Falk Knoch,  

 

期刊: Journal für Praktische Chemie/Chemiker‐Zeitung  (WILEY Available online 1995)
卷期: Volume 337, issue 1  

页码: 38-42

 

ISSN:0941-1216

 

年代: 1995

 

DOI:10.1002/prac.19953370108

 

出版商: WILEY‐VCH Verlag GmbH

 

数据来源: WILEY

 

摘要:

Aryl‐(4‐arylimino‐4H‐pyrido[1,2‐a]pyrazine‐3‐yl)amines‐Synthesis, Complex Formation with Molybdenum(0) and OxygenationThe synthesis of p‐tolyl(4‐p‐tolylimino‐4H‐pyrido [1,2‐a]pyrazine‐3‐yl)amine8(TTPPA) is achieved by the reaction of 2‐pyridylmethylamine with oxalic acid bis(p‐tolylimidoyl)chloride. The ion‐pair [Na(THF)3][(TTPPAH)Mo(CO)4]4is obtained by the reaction of the NH‐acidic compound8with sodium bis(trimethylsilyl)amide and (nor)Mo(CO)4(nor = norbornadiene) dissolved in THF. The bidentate ligand anion TTPPA‐H is related to the 1,4‐diazadienes, but its n‐donor effect is dominating. Its trans‐influence results in different Mo‐CO‐bond lengths of4: 1.901 and 1.951 Å (trans‐positions); 2.003 and 2.031 Å (cis‐positions). In the cationic part of4the sodium is five‐coordinate (distorted tetragonal pyramidal structure). Donor atoms are the three THF, N3 of TTPPA‐H, and the oxygen atom of one CO of the moiety Mo(CO)4.8is oxygenated by hydrogen peroxide or by dioxygen on heating. In the course of a ring transformation of the 6‐membered pyrazine to the 5‐membered imidazole cycle 3‐p‐tolyl‐5‐p‐tolylimino‐2‐pyridine‐2‐yl‐2,3‐dihydro‐imidazol‐4‐one9is formed. In THF two isomers9and9aare observed i

 

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