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A Structural and Theoretical Analysis of Transition Metalloporphodimethenes and Their Relationship with Metalloporphyrins
Author(s) -
Re Nazzareno,
Bonomo Lucia,
Da Silva Carlos,
Solari Euro,
Scopelliti Rosario,
Floriani Carlo
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010618)7:12<2536::aid-chem25360>3.0.co;2-7
Subject(s) - transition metal , reactivity (psychology) , chemistry , density functional theory , nickel , metal , computational chemistry , crystallography , electronic structure , stereochemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
The paper reports the synthesis of the first‐row transition metal hexaethylporphodimethene derivatives [(Et 6 N 4 )M] [M=Mn, 3 ; M=Co, 5 ; M=Cu, 7 ] on a multigram scale, which makes them easily available for reactivity studies. After synthesis they were converted into the corresponding five‐coordinate [(Et 6 N 4 )M(L)] [M=Mn, L=THF, 8 ; M=Co, L=Py, 9 ] and six‐coordinate [(Et 6 N 4 )M(L) 2 ] [M=Mn, L=THF, 10 ; M=Mn, L=Py, 11 ] derivatives. The compounds mentioned above and those recently reported, namely the iron and nickel derivatives 4, 6, 12 , and 13 , permit the presentation of the first coherent report on the structural, optical, magnetic, and electronic characteristics of the first‐row transition metal porphodimethene derivatives. The experimental results, coupled with a detailed theoretical analysis (Density Functional Theory, DFT), give the appropriate background for future development of the porphodimethene skeleton, which paves the way from porphyrinogen to porphyrins. In addition, this report, encompassing the entire first row of transition metal ion porphodimethenes, allows a valuable comparison to be made with the corresponding metallated porphyrins, thus establishing the peculiar differences in terms of structural and electronic properties and potential reactivity.