227008-07-3Relevant academic research and scientific papers
1,8-Diazabicycloundec-7-ene as a ligand in an intermediate in selective carbonyl substitution of a ruthenium-cobalt complex
Regragui, Rachid,Dixneuf, Pierre
, p. C11 - C14 (1988)
1,8-Diazabicycloundec-7-ene, DBU, reacts with (OC)4Ru(μ-PPh2)Co(CO)3 (1) at room temperature to give an intermediate 2, which on protonation in the presence of CO regenerates 1 and on protonation in the presence of PMe3 gives the monosubstituted product (OC)3(L)Ru(μ-PPh2)Co(CO)3 (3 L=PMe3).DBU promotes the selective formation of 4 (L=PPh2Me) or 5 (L=Ph2PCH2C(Me)=CH2) in one-step from 1, Ph2PH, and methyl iodide or methallyl chloride, respectively.
Enhancing the anion affinity of urea-based receptors with a Ru(terpy) 22+ chromophore
Baggi, Giorgio,Boiocchi, Massimo,Ciarrocchi, Carlo,Fabbrizzi, Luigi
, p. 5273 - 5283 (2013/06/26)
Covalent linking of a Ru(terpy)22+ substituent improves recognition and sensing properties of the urea subunit toward anions. Urea's anion affinity is enhanced by the electrostatic attraction exerted by the RuII cation and by the electron-withdrawing effect exerted by the entire polypyridine-metal complex. Such an enhancement of the anion affinity, which results from the combination of a through-space and a through-bond effect, is greater than that exerted by the classical neutral electron-withdrawing substituent nitrophenyl. Small yet significant modifications of π-π* and MLCT bands of the Ru(terpy)22+ chromophore, detected through UV-vis spectrophotometric titrations, allowed the determination of the constants for the formation of receptor-anion H-bond complexes in diluted MeCN solution. On 1H NMR titration experiments, carried out under more concentrated conditions, the interaction of a second Cl- ion was observed, taking place through an outer-sphere mechanism. The Ru(terpy) 22+ substituent favors the deprotonation of a urea N-H fragment on addition of a second equivalent of fluoride, with formation of HF2-.
INFLUENCE OF WATER ON THE KINETICS OF THE REACTION OF NITROALKANES WITH AMINE BASES IN APROTIC SOLVENTS
Galezowski, Wlodzimierz,Jarczewski, Arnold
, p. 679 - 688 (2007/10/02)
The traces of water in reaction systems of nitroalkanes and amine bases in aprotic solvents caused a marked decrease of the reaction rate instead of its acceleration expected from possible triggering of side reactions effected by hydroxide ions or hydroxide ion pairs BH+, OH-.The kinetics and possible consequences in the mechanism of proton transfer are discussed.
