TY - JOUR
AU - Saito, Kazuo
AB - A new complex salt [Ph4P][PtCl3(S,S-tbn[1,3-3H])] (tbn, trans-2-butene) undergoes racemization and ligand isotopic exchange in acetone containing a large excess of tbn without side reactions. Both rates are expressed by the second order rate equations, R(CD)=K2(CD)[Pt][tbn] and R(IE)=K2(IE)[Pt][tbn], the k2 values being 17.6 and 70.6×10−3M−1s−1 at 8.0 °C, respectively (M=mol dm−3). Individual k2 values for the substitutions without and with inversion of configuration of coordinated tbn are calculated to be 62.0 and 8.7×10−3M−1s−1, respectively, the corresponding ΔH\eweq and ΔS\eweq values being 36.3±3.1 and 37.6±2.7 kJ mol−1, and −138±12 and −149±10 J· mol−1 Kr−1. Source of the stereoselectivity appears to consist in the difference in ease of formation of square pyramidal transition state on the nucleophilic attack of tbn upon the complex.
TI - Stereoselective Substitution of trans-2-Butene for the S,S-2-Butene in Trichloro-S,S-2-buteneplatinate(II) in Acetone
JO - Bulletin of the Chemical Society of Japan
DO - 10.1246/bcsj.51.503
DA - 2006-04-19
UR - https://www.deepdyve.com/lp/oxford-university-press/stereoselective-substitution-of-trans-2-butene-for-the-s-s-2-butene-in-C0huVmdSG3
SP - 503
EP - 505
VL - 51
IS - 2
DP - DeepDyve
ER -