Importance of the C-H...N weak hydrogen bonding on the coordination structures of manganese(III) porphyrin complexes.

The reactions between Mn(Por)Cl and Bu(4)N(+)CN(-) have been examined in various solvents by UV-vis and (1)H NMR spectroscopy, where Por's are dianions of meso-tetraisopropylporphyrin (T(i)PrP), meso-tetraphenylporphyrin (TPP), meso-tetrakis(p-(trifluoromethyl)phenyl)porphyrin (p-CF(3)-TPP), meso-tetramesitylporphyrin (TMP), and meso-tetrakis(2,6-dichlorophenyl)porphyrin (2,6-Cl(2)-TPP). Population ratios of the reaction products, Mn(Por)(CN) and Mn(Por)(CN)(2), have been sensitively affected by the solvents used. In the case of Mn(T(i)PrP)Cl, the following results are obtained: (i) The bis-adduct is preferentially formed in dipolar aprotic solvents such as DMSO, DMF, and acetonitrile. (ii) Both the mono- and bis-adduct are formed in the less polar solvents such as CH(2)Cl(2) and benzene though the complete conversion to the bis-adduct is achieved with much smaller amount of the ligand in benzene solution. (iii) Only the mono-adduct is formed in CHCl(3) solution even in the presence of a large excess of cyanide. (iv) Neither the mono- nor the bis-adduct is obtained in methanol solution. The results mentioned above have been explained in terms of the C-H.N and O-H.N hydrogen bonding in chloroform and methanol solutions, respectively, between the solvent molecules and cyanide ligand; hydrogen bonding weakens the coordination ability of cyanide and reduces the population of the bis-adduct. The importance of the C-H.N weak hydrogen bonding is most explicitly shown in the following fact: while the starting complex is completely converted to the bis-adduct in CH(2)Cl(2) solution, the conversion from the mono- to the bis-adduct is not observed even in the presence of 7000 equiv of Bu(4)N(+)CN(-) in CHCl(3) solution. The effective magnetic moments of the bis-adduct has been determined by the Evans method to be 3.2 micro(B) at 25 degrees C, suggesting that the complex adopts the usual (d(xy))(2)(d(xz), d(yz))(2) electron configuration despite the highly ruffled porphyrin core expected for Mn(T(i)PrP)(CN)(2). The spin densities of Mn(T(i)PrP)(CN)(2) centered on the pi MO have been determined on the basis of the (1)H and (13)C NMR chemical shifts. Estimated spin densities are as follows: meso-carbon, -0.0014; alpha-pyrrole carbon, -0.0011; beta-pyrrole carbon, +0.0066; pyrrole nitrogen, -0.022. The spin densities at the pyrrole carbon and meso nitrogen atoms are much smaller than those of the corresponding Mn(TPP)(CN)(2), which is ascribed to the nonplanar porphyrin ring of Mn(T(i)PrP)(CN)(2). This study has revealed that the C-H.N weak hydrogen bonding is playing an important role in determining the stability of the manganese(III) complexes.