Aniline-methane complexes

Such a sequential dissociation mechanism is most likely to be found in polyatomic dimers. Examples which appear to dissociate in this fashion are aniline molecules complexed with either Ar or CH4 (Bernstein, 1990 Nimlos et al., 1989). These two dimers offer an interesting comparison because the number of van der Waals modes in the case of the CH4 partner is 6 while it is only 3 with the Ar as partner. Replacement of the Ar by the methane group will increase and reduce k. ... 

The increased Markovnikov selectivity in the hydroamination of aliphatic terminal alkynes with aniline derivatives seems to be universal for a number of titanium-based hydroamination catalysts, such as Ind2TiMe2 (49) [184], the di-(pyrrolyl) amine complex 50 [186, 187], and the di(pyrrolyl)methane complex 51 [188]. The bis(amidate) titanium complex 43 exhibited enhanced catalytic activity compared to titanocene catalysts, thus combining high a ri-Markovnikov selectivity with high catalytic activity [191]. 

Ni(II)(OAc)2bpy and Co(II)(OAc)2bpy catalyze the Michael addition of nitro-methane, malononitrile, and aniline to a,j8-unsaturated ketones, methyl acrylate, and acrylonitrile in DMF under neutral conditions [116]. FeCls 6H2O is a highly efficient catalyst of Michael reaction of 1,3-dicarbonyl compounds with a,/3-unsaturated ketones under mild and neutral conditions (Sch. 24) [117]. There is literature precedent for this reaction with dual catalysis Ni(II) immobilized on a clay support and FeCl3 to activate the enone [118]. The mechanism proposed for the single-center catalysis involves coordination of the enone to a diketonato complex [119]. The chemo-... 

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