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|Title: ||Synthesis and characterization of phosphorus complexes of meso-tetraphenylporphyrin (tpp), and X-ray crystal structure of [P(tpp)(OCH(CH3)(2))(2)](+)Cl-|
|Issue Date: ||2010-06-29 18:06:35 (UTC+8)|
|Abstract: ||Three cationic phosphorus(V) porphyrin complexes of the type [P(ttp)(L)(2)](+) [tpp = meso-tetraphenylphorphyrin; the axial ligand L = OCH(CH3)(2), O(CH2)(4)OH, O-p-C6H4OH] have been prepared. Al compounds were characterized by H-1 and C-13 NMR and mass spectrometry. The structure of the new compound di(2-propanolato) (meso-tetraphenylporphyrinato)phosphorus (V) chloride, [P(tpp) (OCH(CH3)(2))(2)](+) Cl-, was determined by a single-crystal X-ray structure analysis. The cation of [P(tpp)(OCH (CH3)(2))(2)](+) Cl- displays an octahedral coordination about the phosphorus atom and exhibits a ruffled porphyrin geometry with a core size of 1.866 Angstrom. The displacement of the phosphorus atom from the porphyrin mean plane is 0.016 Angstrom. The geometry around the phosphorus centre of the [P(tpp)(OCH(CH3)(2))(2)](+) Cl- molecule has P(1)-O(1) = 1.650(3) Angstrom, P(1)-O(2) = 1.622(3) Angstrom and P-Np = 1.866(P) Angstrom. NMR spectroscopy provides a convenient method for investigating the ring current effect (Delta delta) between di(1,4-butanediolato) (meso-tetraphenylporphyrinato) phosphorus(V) chloride, [P(tpp) (OCH2 CH2CH2CH2OH)(2)](+) Cl-, with fluxional 1,4-butanediolate ligands, and di(1,4-hydroxybenzeneato) (meso-tetraphenylporphyrinato) phosphorus(V) chloride, [P(tpp)(O-p-C6H4 OH)(2)](+) Cl-, with rigid 1,4-hydroxybenzeneate ligands. It also differentiates the ring current effect for the diolate ligands of [P(tpp) (O(CH2)(n)OH)(2)](+) Cl- with different chain lengths by increasing n from 2 to 4. Copyright (C) 1996 Elsevier Science Ltd|
|Appears in Collections:||[機械工程研究所] 期刊論文|
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