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標題: (I)-用X-光繞射儀、核磁共振(NMR)探討P(TPP)(OCH3)2+Cl分子結 (II)-P(TPP)(OCH3)(OH)+離子的一步水解動力學探討 (III)-用核磁共振儀探討P(TPP)(OCOH)2+的分子結構
(I)X-ray Diffractometer、NMR Studies Molecular Structure of Dimethoxo(Tetraphenylporphyrinato) Phosphorus(v) Chloride (II)The Kinetics of One-step Hydrolysis of Hydroxomethoxo(Tetraphenylporphirinato) Phosphorus(v) Ion (III)NMR Studies Molecular Struct
作者: 許銘桐
關鍵字: X-光繞射儀;水解動力學
出版社: 化學學系
由P(TPP)(OCH3)2+CI-之X-ray結構(part 1,圖1),得知此分子對於磷原子而言是一個正八面體配位幾何形狀,其晶體屬於三斜晶體空間對稱群(triclinic space group)P1, a =12.239(4),,b=12.538(3), c=13.735(3) A, a= 84.36(2), b=84.44(2), g=72.40(2)° and Z=2° X-ray解此結構是使用直接法(Direct method),3357個1>3s(Ⅰ)獨立反射數據精確計算晶體得conventional R 因子0.0646.P-0(1),P-0(2),P-NP之矩離分別為1.634(4),1.630(5),1.825(4)A;而磷分子突出TPP平面0.0834 A。
另一方面,我們應用NMR光譜來探討P(TPP)(OCH3)(OH)+之水解情形。利用CDCI3所含的水份使P(TPP)(OCH3)(OH)+水解成P(TPP)(OH)2+。實驗結果顯示P(TPP)(OCH3)(OH)+是一步水解反應,其絕對速率常數 (absolute-rate constant) k=(2.34±0.23)x10-4S-1M-1。
最後一部份,我們僅以1H,13C,DEPT,2D13C-1H COSY來探討P(TPP)(OCOH)2+的結構。

The title compound dimethoxo (tetraphenyl-porphyrinato) phosphorus (V) chloride, P(tpp)(OMe)2+CI-, has been synthesized and its molecular structure determined by x-ray analysis. The molecule P(tpp)(OMe)2+CI- displays an octahedron coordination geometry for the phosphorus atcm. It crystallized in the triclinic space group pI, with a =12.239(4), b=12.538(3), c=13.735(3) A, a= 84.36(2), b=84.44(2), g=72.40(2)° and Z=2. The structure was solved by direct methods. A total of 3357 unique reflections having Ⅰ> 3 s(Ⅰ) was measured with an automated diffractometer and used to refine the crystal structure to a conventional R factor of 6.46% . The displacement of the phosphorus atom from the porphyrin mean place was 0.0834 A The geometry around the phosphorus centre of the P(tpp)(OMe)2+ CI- molecule has P-O(1) = 1.634(4), P-O(2) = 1.630(5) and P-Np= 1.825(4) A.
The hydrolysis of its derivative hydroxomethoxo (tetraphenyl-porpyrinato) phosphorus(V) ion, P(tpp)(OMe)(OH)+, was studied by NMR spectroscopy. The use of a limited amount of water in CDCI3 allowed the hydrolysis product, dihydroxo(tetraphenylporphyrinato) phosphorus(V) ion, P(tpp)(OH)2+, to be identified. The results show that the hydrolysis is a one-step reaction, with an absolure-rate constant k=(2.34±0.23)x10-4s-1M-1 at 240℃.
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