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首页> 外文期刊>Journal of structural chemistry >Spectroscopic characterization and Ab initio calculations of new diazaphosphole and diazaphosphorinane
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Spectroscopic characterization and Ab initio calculations of new diazaphosphole and diazaphosphorinane

机译：新的重氮磷腈和重氮磷精烷的光谱表征和从头算

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Phosphoryl chloride is used as a starting material to synthesize new diazaphosphole, 4-OCH_3-C_6H_4NHP(O)[4-CH_3-NH-C_6H_3-NH] (1) and diazaphosphorinane, 4-OCH_3-C_6H_4NHP(O)[NH-C_(10)H_6-NH] (2). The products are characterized by ~1H, ~(13)C, ~(31)P NMR, and IR spectroscopy. A high value 2J(PNH) = 17.0 Hz, 17.2 Hz is measured for two non-equivalent NH protons of endocyclic nitrogen atoms in compound 1, while it greatly decreases to 4.5 Hz in 2. Also, great amounts are obtained for two ~2J(P,C) as well as two ~3J(P,C) in the ~(13)C NMR spectrum of 1, but they are zero in 2. Here, the effect of ring strain and ring size on the structural and spectroscopic parameters is observed. The ~(31)P NMR spectra reveal that δ(~(31)P) of compound 1 is far much more downfield (12.63 ppm) relative to that of compound 2 (–10.39 ppm). Furthermore, ab initio quantum chemical calculations are performed to optimize the structures of these molecules by density functional theory (B3LYP) and Hartree-Fock (HF) methods, using the standard 6-31+G** basis set. The stabilization energies are calculated by the equation ΔE_(stabilization) = E_(molecule) – ΣE_i, where i = atom. To obtain the atomic hybridizations, NBO computations are made at the B3LYP/6-31+G** level. Also, by NMR calculations the ~1H, ~(13)C, ~(31)P chemical shifts are obtained and compared with the experimental ones.
机译：磷酰氯用作起始原料来合成新的重氮磷腈4-OCH_3-C_6H_4NHP（O）[4-CH_3-NH-C_6H_3-NH]（1）和二氮杂or烷，4-OCH_3-C_6H_4NHP（O）[NH-C_ （10）H_6-NH]（2）。产品的特征在于〜1H，〜（13）C，〜（31）P NMR和IR光谱。对于化合物1中环内氮原子的两个非等价NH质子，测得的高值2J（PNH）= 17.0 Hz，为17.2 Hz，而在2中则大大降低至4.5 Hz。而且，对于两个〜2J，获得了大量（P，C）以及〜（13）C NMR光谱中的两个〜3J（P，C），但它们在2中为零。这里，环应变和环尺寸对结构和光谱的影响遵守参数。 〜（31）P NMR光谱显示，相对于化合物2（–10.39 ppm），化合物1的δ（〜（31）P）的远场低得多（12.63 ppm）。此外，使用标准的6-31 + G **基集，通过密度泛函理论（B3LYP）和Hartree-Fock（HF）方法，从头进行了量子化学计算，以优化这些分子的结构。稳定能由公式ΔE_（稳定）= E_（分子）–ΣE_i计算，其中i =原子。为了获得原子杂交，在B3LYP / 6-31 + G **级别进行了NBO计算。同样，通过NMR计算，获得了〜1H，〜（13）C，〜（31）P的化学位移，并与实验值进行了比较。

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