Tip-Induced β-Hydrogen Dissociation in an Alkyl Group Bound on Si(001)

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

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Reduction of terphenyl iron(ii) or cobalt(ii) halides in the presence of trimethylphosphine: an unusual triple dehydrogenation of an alkyl group

Dalton Transactions ◽

10.1039/b904647j ◽

2009 ◽

pp. 5401 ◽

Cited By ~ 11

Author(s):

Chengbao Ni ◽

Bobby D. Ellis ◽

Troy A. Stich ◽

James C. Fettinger ◽

Gary J. Long ◽

...

Keyword(s):

Alkyl Group

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MW irradiation and ionic liquids as green tools in hydrolyses and alcoholyses

Green Processing and Synthesis ◽

10.1515/gps-2021-0001 ◽

2020 ◽

Vol 10 (1) ◽

pp. 001-010 ◽

Cited By ~ 1

Author(s):

Nikoletta Harsági ◽

Betti Szőllősi ◽

Nóra Zsuzsa Kiss ◽

György Keglevich

Keyword(s):

Ionic Liquids ◽

Alkaline Hydrolysis ◽

Alkyl Group ◽

Phosphinic Acid ◽

Reaction Times ◽

Alternative Possibility ◽

First Order ◽

Pseudo First Order ◽

Mw Irradiation ◽

Hydrolysis Of

Abstract The optimized HCl-catalyzed hydrolysis of alkyl diphenylphosphinates is described. The reaction times and pseudo-first-order rate constants suggested the iPr > Me > Et ∼ Pr ∼ Bu order of reactivity in respect of the alkyl group of the phosphinates. The MW-assisted p-toluenesulfonic acid (PTSA)-catalyzed variation means a better alternative possibility due to the shorter reaction times, and the alkaline hydrolysis is another option. The transesterification of alkyl diphenylphosphinates took place only in the presence of suitable ionic liquids, such as butyl-methylimidazolium hexafluorophosphorate ([bmim][PF6]) and butyl-methylimidazolium tetrafluoroborate ([bmim][BF4]). The application of ethyl-methylimidazolium hydrosulfate ([emim][HSO4]) and butyl-methylimidazolium chloride ([bmim][Cl]) was not too efficient, as the formation of the ester was accompanied by the fission of the O–C bond resulting in the formation of Ph2P(O)OH. This surprising transformation may be utilized in the phosphinate → phosphinic acid conversion.

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