Abstract
A range of nitrosylmetalloporphyrin complexes, M(porph)NO [M = Fe, Co; porph = TPP, OEP, T[PIV]PP], some labelled with [15]NO, has been synthesised and investigated as structural and spectroscopic models of the cured meat pigment, nitrosylmyoglobin. The nitrosylmetalloporphyrins were found to be unstable in solution (and some in the solid state) with respect to loss or further reaction of the nitrosyl ligand. The diamagnetic cobalt (III) porphyrin nitrosyIs and a range of other square pyramidal complexes of cobalt(III) with an apical nitrosyl ligand have been further investigated by [15]N and [59]Co NMR spectroscopy to establish whether the CoNO group is bent or linear and to study nephelauxetic and spectrochemical effects at the metal. In all cases studied the CoNO group is bent (CoNO ~ 120°). The basal ligands were dithiocarbamate, tetradentate Schiff base, porphyrin, and bidentate diamine and oximate giving S[4], S[2]N[2], N[4], OONN, or ONON coordination in the equatorial plane. The shielding of both cobalt and nitrogen tends to decrease with decrease in M(d) to pi* (NO) back-bonding as indicated by M-N and N-O bond distances, and the MNO angle and the NO stretching frequencies. The shieldings decrease with electron withdrawal by ring substituents and also in going from sulphur to nitrogen to oxygen coligands, i.e. with decrease in ligand field splitting and in the nephelauxetism of the coligands. The bent nitrosyls of cobalt can function as oxygen transfer catalysts via a nitrosyl-nitro couple. Consequently, a range of Co(III) porphyrin nitro complexes, (L)Co(porph)NO[2] (porph = TPP, OEP; L = py, 1Melm) and several nitro complexes containing the other basal ligands have been synthesised and investigated by the [15]N and [59]Co NMR technique. The coordinated nitro ligand is labile and linkage isomerism and ligand exchange have been observed. These observations may be related to the deterioration of cured meat colour which is of importance to the food industry. The crystal structure of (py)Co(TPP)NO[2] is presented; the nitro group of which is rotationally disordered. Recrystallisation of (1MeIm)Co-(TPP)NO[2] gave [Co(TPP)(1Melm)[2]]NO[2], the crystal structure of which has been determined. Formation of this nitrite is further evidence for the lability of the nitro ligand. The known complex Fe(salphen)NO was prepared using ascorbic acid for the first time to prevent contamination with the oxo-bridged iron(III) dimer. Variable temperature [57]Fe Mossbauer effect studies of the S = 1/2 to S = 3/2 spin transition for Fe(salphen)NO show that the crossover is continuous and centred at T[c] ~ 181 K, and that the electronic transition between the two spin states is rapid on the Mossbauer timescale. The fluxionality of CoCl[2]([15]NO)(PPh[2]Me)[2] was studied by variable temperature [15]N and [31]P NMR. An [17]O NMR study of the ?-peroxo complex [(NH[3])[5]Co[17]O[2]Co(NH[3])[5]](NO[3])[4]. 2H[2]O is presented. An attempt to measure [15]N NMR spectra of the diamagnetic 18 electron species, Fe(porph)([14]NO)([15]NO) (porph = TPP, OEP) presumably containing linear FeNO[+] and bent FeNO[-] was unsuccessful.