How to Stabilize η3-Silapropargyl/Alkynylsilyl Complex of [CpL2M]+(L = CO, PMe3, or PF3 and M = W or Mo): Theoretical Prediction
How to Stabilize η3-Silapropargyl/Alkynylsilyl Complex of [CpL2M]+(L = CO, PMe3, or PF3 and M = W or Mo): Theoretical Prediction
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DOI：
10.1021/om8006163
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发表时间：
2009-01
期刊：
影响因子：
2.8
通讯作者：
M. Ray;Y. Nakao;Hirofumi Sato;H. Sakaba;S. Sakaki
中科院分区：
文献类型：
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作者：
M. Ray;Y. Nakao;Hirofumi Sato;H. Sakaba;S. Sakaki
本文从理论上研究了一种新的过渡金属η3-硅炔丙基/炔基硅烷基配合物CpL 2 M（η3-R22 SiCCR 1）（M = W或Mo; L = CO，PMe 3，或PF 3; Cp = C5 H5; R1 = H，Me，tBu，或CF 3; R2 = H，Me，或F）的稳定性。虽然该配合物在实验中被提议作为合成钨乙炔-亚甲硅烷基配合物Cp（CO）2 W（CCtBu）（SiPh 2）的中间体，但它尚未被合成。从理论计算与DFT方法，我们希望提出的组合，吸电子的CF 3的C，σ-吸电子/π-给电子的F的Si，Mo中心，和CO是最好的稳定η3-硅炔丙基/炔基甲硅烷基形式。然而，C上的大体积tBu，Si上的H或Me，W中心和PMe 3的组合是最好的稳定乙炔基-甲硅烷基形式，这也是一个有趣的物种。原因在此讨论。
We theoretically investigated here how to stabilize a new transition metal η3-silapropargyl/alkynylsilyl complex CpL2M(η3-R22SiCCR1) (M = W or Mo; L = CO, PMe3, or PF3; Cp = C5H5; R1 = H, Me, tBu, or CF3; R2 = H, Me, or F) which is an interesting silicon analogue of a transition metal η3-propargyl complex. Though this complex was experimentally proposed as an intermediate in the synthesis of a tungsten acetylide−silylene complex Cp(CO)2W(CCtBu)(SiPh2), it has not been synthesized yet. From theoretical computations with DFT method, we wish to propose that the combination of electron-withdrawing CF3 on C, σ-electron-withdrawing/π-electron-donating F on Si, Mo center, and CO is the best to stabilize the η3-silapropargyl/alkynylsilyl form. However, the combination of bulky tBu on C, either H or Me on Si, W center, and PMe3 is the best to stabilize the acetylide−silylene form, which is also an interesting species. The reasons are discussed herein.