Superamidines 2.: Synthesis of the bulky ligand N,N′-bis-(2,6-diisopropylphenyl)-trifluoroacetamidine and its molybdenum carbonyl complex

被引:21
|
作者
Boeré, RT [1 ]
Klassen, V
Wolmershäuser, G
机构
[1] Univ Lethbridge, Dept Chem, Lethbridge, AB T1K 3M4, Canada
[2] Univ Kaiserslautern, Fachbereich Chem, D-67663 Kaiserslautern, Germany
关键词
trifluoromethyl; superamidine; amidine; molybdenum; carbonyl; coordination;
D O I
10.1139/cjc-78-5-583
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
N,N'-bis-(2,6-diisopropylphenyl)trifluoroacetamidine has been prepared for the first time from 2,6-diisopropylaniline and the trifluoroacylation reagent TFAP via the imidoylchloride. The crystal structure of the amidine was determined, indicating that it crystallizes in the Z-anti tautomer, in contrast to the nonfluorinated analogue, which is Z-anti in the solid state. In solution, as indicated by NMR spectroscopy, it exists in two isomeric forms. The amidine reacts with Mo(CO)(6) to produce a coordination complex with Mo(CO)(3) in which the ligand is also in the Z-anti geometry, the metal is eta(6)-coordinated to the imino-2,6-diisopropylphenyl ring, and the amino N-H unit is directed towards the metal, as determined by a single-crystal X-ray structure. Unlike the analogous nonfluorinated acetamidine, there is no indication of an intermediate in which the neutral amidine is coordinated in a monodentate fashion to an Mo(CO)(5) unit, which we now attribute to the predominant geometry of the ligand, both in the solid state and in solution, being Z-anti. The high steric bulk of this superamidine ligand apparently prevents the formation of a metal-metal bonded Mo-2(amidinate)(4) as observed previously in a redox reaction between N,N'-diphenylbenzamidine and Mo(CO)(6) under similar thermal reaction conditions.
引用
收藏
页码:583 / 589
页数:7
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