文献类型：期刊文献

英文题名：The Cyanate and 2-Phosphaethynolate Anion Congeners ECO- (E = N, P, As, Sb, Bi): Prelude to Experimental Characterization

作者：Lu, Yunxiang[1,2];Wang, Hui[3];Xie, Yaoming[4];Liu, Honglai[1,2];Schaefer, Henry F.[4]

机构：[1]E China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Dept Chem, Shanghai 200237, Peoples R China;[3]Southwest Jiaotong Univ, Sch Phys Sci & Technol, Chengdu 610031, Peoples R China;[4]Univ Georgia, Ctr Computat Quantum Chem, Athens, GA 30602 USA

年份：2014

卷号：53

期号：12

起止页码：6252

外文期刊名：INORGANIC CHEMISTRY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000337557800046)】；

基金：This work was supported by the National Natural Science Foundation of China (21103047) and the Fundamental Research Funds for the Central Universities of China. This research at Georgia is supported by the U.S. National Science Foundation (Grant No. CHE-1361178).

语种：英文

摘要：Pioneering synthetic research by the groups of Grutzmacher and Goicoechea have made possible the preparation of 2-phosphaethynolates (PCO-). The obvious question arises: can progress be made toward AsCO-, SbCO-, and BiCO-? Here the properties of all five anion congeners ECO- (E = N, P, As, Sb, Bi) were systematically investigated using ab initio coupled-cluster methods with correlation-consistent basis sets cc-pVXZ (X = D, T, Q). These anions exhibit linear structures with significant natural bond orbital negative charge on both the E and 0 atoms. These species should react with electrophiles via attack at either center. On going from nitrogen to bismuth, with the atomic radius increasing, the bond between E and C becomes weaker, while the C-O bond tends to be slightly stronger. By the time one gets to BiCO-, the C-O bond distance is 1.181 angstrom, indicating a very strong double bond. Relative to the PCO- anion, which is reactive toward several unsaturated compounds, the As/Sb/BiCO- anions may undergo cycloaddition more readily with unsaturated substrates. The dissociation energy of the E C bond, except for that of NCO-, is predicted to be much less than that of the C-O bond. These dissociation energies are 76 kcal/mol (P--CO), 58 kcal/mol (As--CO), 37 kcal/mol (Sb--CO), and 28 kcal/mol (Bi--CO). Even the BiCO- anion should be achievable in the laboratory. The vibrational frequencies for these anions are predicted, and our results should assist in the experimental characterization and exploration of the heavier congeners ECO-.