201053-96-5Relevant academic research and scientific papers
Quantitative determination of the regioselectivity of nucleophilic addition to η3-propargyl rhenium complexes and direct observation of an equilibrium between η3-propargyl rhenium complexes and rhenacyclobutenes
Casey, Charles P.,Boiler, Timothy M.,Samec, Joseph S. M.,Reinert-Nash, John R.
, p. 123 - 131 (2009/05/30)
PMe3 adds selectively to the central carbon of the η3-propargyl complex [C5Me5(CO) 2Re(η3-CH2C=CCMe3)][BF 4] (1-t-Bu) to form the metallacyclobutene [C
Kinetic addition of nucleophiles to η3-propargyl rhenium complexes occurs at the central carbon to produce rhenacyclobutenes
Casey, Charles P.,Nash, John R.,Yi, Chae S.,Selmeczy, Anthony D.,Chung, Steven,Powell, Douglas R.,Hayashi, Randy K.
, p. 722 - 733 (2007/10/03)
Kinetic addition of nucleophites occurs at the center carbon of η3-propargyl rhenium complexes to produce rhenacyclobutenes. Reaction of P(CH3)3 with C5Me5(CO)2Re[η3-CH2C≡CC(CH3)3]+BF4- (3a) gave the metallacyclobutene C5Me5(CO)2ReCH2C(PMe3)=CC(CH3)3+BF4- (4a), which was characterized by X-ray crystallography. Malonate and acetylide nucleophiles reacted with C5Me5(CO)2Re[η3-CH2C≡CCH3]+PF6- (3b) to give metallacyclobutene complexes. Pyridine added to the central propargyl carbon of 3b at low temperature to produce the metastable metallacyclobutene C5Me5(CO)2ReCH2C(NC5H5)=CCH3+PF6- (14b) which rearranged to the η2-allene complex C5Me5(CO)2Re[η2-H2C=C=C(NC5H5)CH3]+PF6- (15K) at room temperature. 4-(Dimethylamino)pyridine (DMAP) added to the central carbon of the tert-butyl-substituted η3-propargyl complex 3a below -38°C to give the rhenacyclobutene complex C5Me5(CO)2ReCH2C-C(NC5H4NMe2)=CC(CH3)3+BF4- (22a) which rearranged to the η2-alkyne complex C5Me5(CO)2Re[η2-(CH3)3-CC≡CCH2NC5H4NMe2]+BF4- (23) at room temperature. Reaction of water with C5Me5(CO)2Re[η3-CH2C≡CH]+BF4-(3c) gave the hydroxyallyl complex C5Me5(CO)2Re[η3-CH2C(OH)CH2]+BF4- (29) by a process proposed to involve nucleophilic addition of water to the central propargyl carbon of 3c followed by protonation of the metallacyclobutene intermediate.
