Theoretical Study of Phosphoryl Transfer Reactions

摘要

The energetics and transition state (TS) structures of the reactions of six substrates, RSUB1/SUBRSUB2/SUBP(=O or S)Cl-typeBRwhere RSUB1/SUB = RSUB2/SUB = Me and/or MeO, with ammonia in acetonitrile are theoretically investigated at the level ofBRCPCM-MP2/6-31+G(d) and CPCM-MP2/6-311+G(3df,2p). The degrees of distortion of TS from the idealBRtrigonal bipyramidal pentacoordinate, ΔδSUB≠b/SUB for a backside and ΔδSUB≠f/SUB for a frontside attack, are calculated. TheBRresults of calculation suggest that the feasibility of a frontside attack for P=S is greater than that for P=O systemBRwhen the two ligands, RSUB1/SUB and RSUB2/SUB, becomes larger. The experimental and calculated results of anilinolyses ofBRRSUB1/SUBRSUB2/SUBP(=O or S)Cl-type show the consistent tendencies.