GAS-PHASE AND COMPUTATIONAL STUDIES OF PENTACOORDINATE SILICON
GAS-PHASE AND COMPUTATIONAL STUDIES OF PENTACOORDINATE SILICON
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DOI：
10.1021/ja00228a001
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发表时间：
1988-09-28
影响因子：
15
通讯作者：
GORDON, MS
中科院分区：
文献类型：
--
作者：
DAMRAUER, R;BURGGRAF, LW;GORDON, MS
我们已经证明，多种五配位硅阴离子（硅酸盐）应该是稳定的，并且可以通过结合 MNDO 的预测能力和从头计算方法以及流动余辉 (FA) 实验技术来制备。 MNDO 已用于计算 91 种硅酸盐的阴离子亲和力；除五个外，所有这些预计在阴离子损失方面都是稳定的。 FA 已制备并研究了 24 种硅酸盐，其中大部分以前未报道过。 MNDO 的预测总体上与实验结果以及 Corriu 及其同事之前报告的趋势一致，但在某些情况下发现存在缺陷。例如，MNDO 往往会低估含氟硅醇盐的稳定性。在这些情况下，我们进行了全面计算，发现这些计算与此处报告的实验研究和 Corriu 趋势一致。
We have demonstrated that a wide variety of pentacoordinate silicon anions (siliconates) should be stable and can be prepared by combining the predictive powers of MNDO and ab initio computational methods and the flowing afterglow (FA) experimental technique. MNDO has been used tocompute the anion affinities of 91 siliconates; all but five of these are predicted to be stable with respect to the loss of an anion. Twenty-four siliconates, most of them previously unreported, have been prepared and studied in the FA. The MNDO predictions were, in general, consistent with the experimental results and with trends previously reported by Corriu and co-workers, but in some cases they were found deficient. For example, MNDO tends to underestimate the stability of fluorine-containing siliconates. In these cases, we have carried outab intio computations and found these to be consistent with boththe experimental studies reported here and the Corriu trends.