NMR and EPR spectroscopic and structural studies of low-spin, (d(xz),d(y)(z))(4)(d(x)(y))(1) ground state Fe(III) bis-tert-butylisocyanide complexes of dodecasubstituted porphyrins

Inorganic Chemistry
L Yatsunyk, F A Walker

Abstract

The bis-(1,1-dimethylethylisocyanide) (tert-butylisocyanide) complexes of three iron porphyrinates (2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin, OETPP; 2,3,7,8,12,13,17,18-octamethyl-5,10,15,20-tetraphenylporphyrin, OMTPP; and 2,3,7,8,12,13,17,18-tetra-beta,beta'-tetramethylene-5,10,15,20-tetraphenylporphyrin, TC(6)TPP) have been prepared and studied by EPR and (1)H NMR spectroscopy. From EPR and NMR spectroscopic results it has been found that the ground states of the bis-(t-BuNC) complexes of OETPP, OMTPP, and TC(6)TPP are represented mainly (99.1-99.4%) as (d(xz,)d(yz))(4)(d(xy))(1) electron configurations, with an excited state lying 700 cm(-)(1) to higher energy for the OMTPP complex, and probably at lower and higher energies, respectively, for the OETPP and TC(6)TPP complexes. In the (1)H NMR spectra the (d(xz,)d(yz))(4)(d(xy))(1) electron configurations of all three complexes are indicated by the large and positive meso-phenyl-H shift differences, delta(m)-delta(o) and delta(m)-delta(p), and close to the diamagnetic shifts of groups (CH(3) or CH(2)) directly attached to the beta-carbons. However, in comparison to meso-only substituted porphyrinates such as [FeTPP(t-BuNC)(2)]ClO(4), the meso-phenyl shift...Continue Reading

Citations

Jun 23, 2015·Inorganic Chemistry·Jianfeng LiW Robert Scheidt
Jan 4, 2008·Journal of Inorganic Biochemistry·Mikio NakamuraAkira Ikezaki
Dec 15, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Pablo J AlonsoConrado Rillo
Feb 7, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Yoshiki OhgoMikio Nakamura
Feb 9, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Weilin ChenZhiming Zhang
Jul 4, 2006·Inorganic Chemistry·Mar Gómez-GallegoJuan J Lucena

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