Design for Novel Organo Hypervalent Compounds

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Porphyrin complexes of group 15 : A equilibrium mixture of [(OEP)P(R)(OH)]^4Cl^-(10) and (OEP)PR(=O)(1)was obtained by the reaction of RPCl_2(R=Me, Et, Ph) and (OEP)H_2. Since the acidity of the OH group in 10 is high, 1 and 10 are selectively isolated by controlling pH for the solution of the mixture. The existence of P=O double bond in 1 is confirmed by the X-ray structural dctermination. (OEP) As (R)(=O)(14) is also obtained via [(OEP)As(R)(OH)]^<6+>X^- (13). 13 is the first arsenic porphyrin whose molecular structure is confirmed by X-ray crystallography. The acid-base equibrium between 14 and 13 is also observed. NMR indicates that the acidity of 13 is weaker than that of 10. The heterobimetallic μ-oxo porphyrins [(OEP)Al-O-E(OEP)(R)] (E=P, As) are derived by the reaction of [(OEP)Al(Me)] and the hydroxo porphyrins. The corresponding Al-Sb dinuclear porphyrin is obtained by a photo reaction. The formation of exciplex under the irradiation of light is suggested. ^<121>Sb Mossbauer … More spectra for Sb-TPP complexes indicate that the electronic state of Sb is strongly affected by the axial ligands.Novel hypervalent pentacoordinate carbon and boron compounds : A stable pentacoordinate carbon compound [(MeO)_2C(DMA)]^+ having a 1,8-dimethoxyanthracene ((DMA)H) as a tridentate ligand is firstly isolated. The X-ray analysis definitely indicates the existence of O-C-O hypervalent bond and the density function theory (DFT) calculation also indicates the bonding interaction between C-O bond. The hypervalent pentacoordinate boron compound [(CAT)B(DMA)] (CAT=catecolate anion) is also prepared and fully specificated using an X-ray determination, ^<11>B NMR and a DFT calculation. Employing the van Koten type ligand as a flexible ligand, the second example of hypervalent carbon contpound is obtained and characterized.anti-apicophilic phosphoranes : The anti-apicophilic spirophosphoranes having two Martin ligands (2 : O-cis) are obtained as kinetic products. 2 is highly nucleophilic compared to the apicophilic isomer (O-trans). The acidity of α-proton is high for 2, and by the reaction of its anion and benzaldehyde a hexacoordinate compound, being the intermediate species for Wittig reaction, is derived. No such a product is obtained for apicophilic isomer. Less