Synthesis of Metallo-Deuteroporphyrin Derivatives
and the Study of Their Biomimetic Catalytic Properties
183
system. It is important to point out that with the same electron-donating substituents, the
different activities between the DPDME and other porphyrin diesters may attribute to steric
effect, and the bulky groups are not beneficial to form the μ-oxo dimmer.
catalyst t (h) C (%) S (%) n(Alcohol)/n(Ketone) TON
Co(II)(DPDME) 3.5 18.6 86.4 1.1 85147
Co(II)(DPDEE) 4.0 17.7 83.4 0.9 81026
Co(II)(DPDPE) 4.0 16.1 86.6 1.0 74512
Co(II)(DPDOE) 4.0 15.0 85.8 0.9 69422
Co(II)(DBP) 3.5 17.9 92.1 6.5 82842
Co(II)(DPDNE) 3.0 16.1 86.6 8.0 74512Table 6. Results of the oxidation of cyclohexane catalyzed by modified 13,17-modified
M(DPD). Reaction conditions: cyclohexane 1000 mL, catalyst 0.02 mmol, temperature 150 Ԩ,
pressure 0.8 MPa.
5.5 Oxidation of cyclohexane catalyzed by disulphide-derivatised metallo-
deuteroporphyrins
Two types of disulphide-derivatised M(DP) were used as catalysts for the oxidation of
cyclohexane with air in the absence of additives and solvents. Fig. 14 shows how the yield of
cyclohexanol and cyclohexone changes with time catalyzed by disulphide-derivatised
M(DP). Compared with Co(II)DPDME, all the disulphide-derivatised M(DP) complexes
exhibit higher catalytic activity. The maximum yield of cyclohexanol and cyclohexanone for
Co(II)PDTEP as catalyst in the oxidation of cyclohexane under the conditions of 150 Ԩ and
0.8 MPa reaches to 26%. When the centre metal of the disulphide-derivatised M(DP)
complexes were different, the yields of alcohol and ketone are dissimilar and the following
order of reactivity was observed: Co(II)> ClMn(III)> ClFe(III).
01234560481216202428Yield %time (h)Co(II)DPDME
Co(II)PDTEP
Mn(III)PDTEP
Fe(III)PDTEP
Co(II)DSPPFig. 14. Yields of cyclohexanol and cyclohexanone in the oxidation of cyclohexane catalyzed
by disulphide-derivatised M(DP). Reaction conditions: cyclohexane 1000 mL, catalyst 0.02
mmol, temperature 150 Ԩ, pressure 0.8 MPa.