Aluminum-phosphorus triple bonds: Do substituents make Al equivalent to P synthetically accessible?

作者：Lu Jia Syun; Yang Ming Chung; Su Ming Der^*

来源：Chemical Physics Letters, 2017, 686: 60-67.

DOI：10.1016/j.cplett.2017.08.032

The effect of substitution on the potential energy surfaces of triple-bonded RAl equivalent to PR (R = F, OH, H, CH3, SiH3, SiMe(SitBu(3))(2), SiiPrDis(2), Tbt (C6H2-2,4,6-{CH(SiMe3)(2)}(3)), and Ar* (C6H3-2,6-(C6H2-2,4,6-i-Pr-3)(2))) compounds was investigated by using the theoretical methods (i.e., M06-2X/Def2-TZVP, B3PW91/Def2-TZVP, B3LYP/LANL2DZ+dp, and CCSD(T)). The theoretical examinations reveal that all of the triple-bonded RAl equivalent to PR species prefer to adopt a bent form with a roughly perpendicular bond angle (angle Al-P-R). In addition, the theoretical evidence demonstrates that only the bulkier substituents can efficiently stabilize the central Al equivalent to P triple bond. Moreover, the theoretical analyses (the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) indicate that the bonding characters of the triply bonded RAl equivalent to PR molecules should be described as R'Al(sic)PR'. That is to say, the Al equivalent to P triple bond contains one conventional sigma bond, one conventional pi bond, and one donor-acceptor pi bond. Nevertheless, the theoretical conclusions based on the poor overlap populations between Al and P elements suggest the Al equivalent to P triple bond in such an acetylene analogues (RAl equivalent to PR) is likely to be very weak.

• 出版日期2017-10-16