ISSN:
0947-6539
Keywords:
heterocycles
;
heteroporphyrins
;
nickel
;
porphyrinoids
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The nickel(I) and nickel(II) complexes of 5,20-bis(p-tolyl)-10, 15-diphenyl-21-oxaporphyrin (ODTDPPH) and 5,10,15,20-tetraphenyl-21, 23-dioxaporphyrin (O2TPP) have been investigated. These oxa analogues of 5,10,15,20-tetraarylporphyrin, where one or two pyrrole rings are replaced by a furan moiety, have been synthesized by condensation of the respective precursors, namely 2,5-bis(arylhydroxymethyl)furan, pyrrole, and arylaldehyde. Insertion of nickel(II) into ODTDPPH or O2TPP yielded high-spin five- and six-coordinate ([(ODTDPP)NiIICl] and [(O2TPP)NiIICl2]) complexes, which can be reduced with moderate reducing reagents. The EPR spectra of [(ODTDPP)NiI] and [(O2TPP)NiICl] revealed the NiI oxa(dioxa)porphyrin rather than a NiI anion radical electronic structure. In the structures of [(ODTDPP)NiIICl], [(O2TPP)NiIICl2], and [(ODTDPP)NiI], determined by X-ray diffraction, the furan ring is planar and coordinates in the η1 fashion through the trigonal oxygen atom; the nickel ion lies in the furan plane for the latter two complexes, but slightly outside it in [(ODTDPP)NiIICl]. The Ni-N and Ni-O bond lengths decrease upon reduction of high-spin five-coordinate [(ODTDPP)NiIICl] to four-coordinate [(ODTDPP)NiI]. The pattern of downfield pyrrole resonances in 1H NMR spectra of [(ODTDPP)NiIICl] and [(O2TPP)-NiIICl2] has been established. The downfield positions of furan resonances are unusual for NiII heteroporphyrins; they have been accounted for by the nearly in-plane coordination of the furan moiety as opposed to the side-on coordination found for thiophene- or selenophene-containing heteroporphyrins. An example of ion-pair formation, [(O2TPPH)2][NiIICl4], was produced from [(O2TPP)NiIICl2] by acidification with HCl.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19970030216
