Effect of N-alkylation on the rate of β-amine elimination from transients with CuII-carbon σ bonds

Sara Goldstein, Gidon Czapski, Haim Cohen, Dan Meyerstein, Sason Shaik

نتاج البحث: نشر في مجلةمقالةمراجعة النظراء

10 اقتباسات (Scopus)

ملخص

The rates of β-amine elimination from CuII-CH(CH2NH3)3+2 and CuII-CH2CH2NH2+3 have been found to be about two orders of magnitude lower than those from CuII-CH[CH2N(CH3)2H]3+2 and CuII-CH2CH2N(C2H5) 2H2+ in aqueous solutions. The results indicate that N-alkylation increases the rate of β-amine elimination, whereas previous results demonstrated that O-alkylation decreases the rate of β-elimination of HOR′ from (H2O)5CrIII - CH2CH2OR′2+ (R′ = H, C2H5). These opposite trends are in accord with expectations based on the assumption that the rate of β elimination of X- from LmM(n + 1)-CR1R2CR3R4Xn+ is correlated to the C-X bond strength. A mechanism of activation from the reaction is formulated, based on the Shaik-Pross curve-crossing model. The model provides a basis for the assumption of bond strength controlled rates.

اللغة الأصليةالإنجليزيّة
الصفحات (من إلى)4045-4051
عدد الصفحات7
دوريةPhysical Chemistry Chemical Physics
مستوى الصوت89
رقم الإصدار22
المعرِّفات الرقمية للأشياء
حالة النشرنُشِر - 1993
منشور خارجيًانعم

بصمة

أدرس بدقة موضوعات البحث “Effect of N-alkylation on the rate of β-amine elimination from transients with CuII-carbon σ bonds'. فهما يشكلان معًا بصمة فريدة.

قم بذكر هذا