Reactivity of Ruthenium Allenylidene Complexes with Hydrazines:Formation of Acrylonitrile Complexes

doi:10.6023/cjoc201804023

Abstract

The cationic ruthenium allenylidene complexes[RuCl(=C=C=CR₂)(DPPQ)₂] [BPh₄] (3a:R=Ph; 3b:CR₂=FN=9H-fluoren-9-ylidene) supported by the heterobidentate P,N-donor ligand 8-(diphenylphosphanyl)quinoline (DPPQ) have been synthesized from the reactions of the dimeric complex[Ru(μ-Cl)(DPPQ)₂]₂[BPh₄]₂ (1) with excess 1,1-diphenylprop-2-yn-1-ol (2a) or 9-ethynyl-9H-fluoren-9-ol (2b), respectively. Addition of hydrazines to the ruthenium-allenylidenes 3 led to the facile formation of ruthenium-bound acrylonitrile complexes[RuCl(N≡C-CH=CR₂)(DPPQ)₂] [BPh₄] (4a:R=Ph; 4b:CR₂=FN) at room temperature. This reaction involves the intermolecular nucleophilic attack of hydrazines at the C_α atom of the allenylidene ligand, which represents the first examples of addition of hydrazines to metal-allenylidenes affording acrylonitrile derivatives. Reaction of acrylonitrile complex 4 with an excess of propargyl alcohols 2a or 2b (4 equiv.) could release the organic acrylonitriles 3,3-diphenylacrylonitrile (5a) or 2-(9H-fluoren-9-ylidene)-acetonitrile (5b) along with regeneration of allenylidene complex 3. In addition, the catalytic activity of 1 for the transformation of terminal propargyl alcohols and hydrazines into acrylonitriles has been investigated preliminarily. The results showed that the catalytic reaction did proceed to give the desired acrylonitrile products, albeit the yield not good. Nevertheless, our results of the catalytic reactions demonstrated that it is very promised to develop new catalytic reactions for the transformation of terminal propargylic alcohols and hydrazines into acrylonitriles via allenylidene intermediates.

Key words: ruthenium, allenylidene, alkyne, hydrazine, nitrile

Cite this article

Cai Tao, Yang Yu, Zhang Li, Wen Tingbin. Reactivity of Ruthenium Allenylidene Complexes with Hydrazines:Formation of Acrylonitrile Complexes[J]. Chin. J. Org. Chem., 2018, 38(8): 2017-2027.

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