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Year : 2020, Volume : 10, Issue : 2
First page : ( 129) Last page : ( 137)
Print ISSN : 2231-3907. Online ISSN : 2231-3915. Published online : 2020  05.
Article DOI : 10.5958/2231-3915.2020.00024.3

Synthesis and Characterizarion of Copper (II) and Copper (III) Complexes of Pyrrole-Appended Oxacarbaporphyrin

Kumar Rajeev1,*, Sharma Sivadhar1

1Department of Chemistry, Magadh University, Bodhgaya - 824234.

*Corresponding Author E-mail:

Received:  11  ,  2020; Accepted:  10  December,  2020.

Abstract

The reaction of an O-confused porphyrin with a pendant pyrrole 4 and copper (II) acetate yields an organocopper- (III) diamagnetic complex 4-Cu (III) substituted at the C (3) position by the pyrrole and H. The transformation of 4-Cu (III), performed in aerobic conditions, gave a rare copper(II) organometallic compound 6-Cu(II). In the course of this process, the tetrahedral-trigonal rearrangement originated at the C (3) atom but effects the whole structure. The electron paramagnetic resonance spectroscopic features correspond to a copper (II) oxidation state. A crystallographic analysis of 6-Cu (II) confirmed the formation of a direct metal-C bond [Cu(II)-C 1.939(4) A]. It was found that the Cu (II) complex of O-confused oxaporphyrin is sensitive to oxidative conditions. The degradation of 6-Cu(II) to yield copper(II) tripyrrinone complexes has been observed, which was considered as a peculiar case of dioxygen activation in a porphyrin-like environment. This process is accompanied by regioselective oxygenation at the inner C to form the 2-oxa-3-(2¢-pyrrolyl)-21-hydroxy carbaporphyrinato copper (II) complex ((pyrr)OCPO)CuII (8). The reaction of 6-Cu (II) with hydrogen peroxide, performed under heterophasic conditions, resulted in quantitative regioselective hydroxylation centered at the internal C (21) atom, also producing 8. Treatment of 8 with acid results in demetalation to form the nonaromatic 21 -hydroxy O-confused porphyrin derivative ((pyrr) OCPOH)H (9).

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