| Summary: | 碩士 === 國立中正大學 === 化學學系 === 83 ===
A series of C3v ligands containing Tt-accepting coordination atoms were synthesized by modification of reported procedures. These ligands are listed as following: P (2-py) 3 (A), HO-C (2-py) 3 (B), P (2-HS-C6H4) 3 (C), 1, 3, 5- (HOCH2)3-C6H3 (D), 1, 3, 5-(HSCH2) 3-C6H3 (E). The compounds, M (CO) 3 (CH3CN) 3, where M=Cr and W were also prepared by literature known procedures.
Treatment of one equiv. of P (2-py) 3 (A) with M(CO)3(CH3CN)3 in CH3CN give products of the type, MP (2-py) 3 (CO) 3, where M=Cr and W. However, when Mo (CO) 6 was treated directly with one equiv. of P (2-py) 3, the same type of complex, MoP (2-py) 3 (CO) 3 was formed. The data obtained form 1H, 31P NMR, Infared and mass spectroscopic analyses as well as the elemental analyses are all consistent with the fac-octahedral geometry for the complexes MP (2-py) 3 (CO) 3. Compounds MoP (2-py) 3 (CO) 3 and WP (2- py) 3 (CO) 3 will undergo further reactions with two equiv. of NOBF4 in CH3CN solution to produce cationic metal complexes of the type [P(2-py) 3M (NO) 2 (CO)] (BF4)2. Facile losses of CO were observed for both molybdenum and tungsten ionic complexes in either acetone or CHaCN solutions.
Lithiation of ligands (D) and (E) give compounds 1, 3, 5-(LiXCH2)3-CeHs, where X =0 and S. The compound W [1, 3, 5-(LiOCH2) 3-C6H3] Cl3 was isolated from the reactions of WCl6 and 1, 3, 5-(LiOCH2)3-C6H3 in diethyl ether solution.
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