Six-coordinate nitrosyl and nitro complexes of meso-tetratolylporphyrinatocobalt with trans sulfur-donor ligands.
By Fourier transform infrared and optical spectroscopy, it has been observed that interactions of dimethyl sulfide and tetrahydrothiophene with nitrosyl and nitro complexes of meso-tetra-p-tolylporphyrinatocobalt [Co(TTP)] lead to the formation of previously unknown six-coordinate species. Nitrosyl complexes of the general formula (S-donor)Co(TTP)(NO) are thermally unstable and can be seen only at low temperatures both in the solid state and in solution. The nitro complexes (S-donor)Co(TTP)(NO(2)) are fairly stable at room temperature in the solid state but partly decompose upon dissolution. The binding constants for these complexation reactions were determined. In contrast to the solid-state iron nitritoporphyrin complexes, oxo-transfer reactions from the coordinated nitro group of Co(TTP)(NO(2)) to the S donors, resulting in oxidation of these sulfides and the formation of Co(TTP)(NO), were not observed.
Kurtikyan
Tigran S
TS
Molecule Structure Research Center of Scientific and Technological Center of Organic and Pharmaceutical Chemistry NAS, 26 Azatutyan av., 375014 Yerevan, Armenia. kurto@netsys.am
Gulyan
Gurgen M
GM
Dalaloyan
Arina M
AM
Kidd
Bryce E
BE
Goodwin
John A
JA
D003035:Cobalt / Q000737:chemistry*; D008024:Ligands; D008665:Metalloporphyrins / Q000737:chemistry*; D009574:Nitro Compounds / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013440:Sulfides / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry; D013876:Thiophenes / Q000737:chemistry*
D008024:Ligands; D008665:Metalloporphyrins; D009574:Nitro Compounds; D009589:Nitrogen Oxides; D013440:Sulfides; D013876:Thiophenes; D003035:Cobalt; D013455:Sulfur; C121030:tetrahydrothiophene; C004784:dimethyl sulfide