Two organometallic complex fragments with 5d6 configurated metal centers of different character, electrophilic IrIIICp*Cl+ and p-donating ReI(CO)3Cl, were used as probes in compds. contg. 1,3-dimethyllumazine (DML), 1,3-dimethylalloxazine (DMA), 2-pivaloylpterin (PP) and 6-methyl-2-pivaloylpterin (MPP) as biochem. relevant ligands. Evidence from spectroscopy (NMR, IR, UV-visible) in aprotic solvents points in most cases to the O4 and N5 atoms as chelate donors for metal binding. For (DMA)IrIIICp*Cl(PF6) this was substantiated by a crystal structure anal. With PP, however, an Ir(III) compd. with pivaloyl-coordinated metal was obtained. Whereas both the IrIII and Re1 complexes of the good p acceptor ligand DMA can be reduced reversibly and thus studied by (spectro)electrochem. (IR, UV-visible, EPR: ligand-centered 1-electron redn.), the DML system exhibits such behavior only for the IrIII species. The complexes of the 2-pivaloylpterins showed only irreversible redn. on SciFinder(R)
%0 Journal Article
%1 Heilmann.1999
%A Heilmann, Oliver
%A Hornung, Fridmann M.
%A Fiedler, Jan
%A Kaim, Wolfgang.
%D 1999
%J Journal of Organometallic Chemistry
%K alloxazine complex complex;ESR complex;electrochem complex;iridium crystal cyclopentadienyl dimethylalloxazine electrochem iridium pivaloylpterin prepn redn redn;rhenium rhenium structure
%N 1
%P 2--10
%R 10.1016/S0022-328X(99)00294-6
%T Organometallic iridium(III) and rhenium(I) complexes with lumazine, alloxazine and pterin derivatives
%V 589
%X Two organometallic complex fragments with 5d6 configurated metal centers of different character, electrophilic IrIIICp*Cl+ and p-donating ReI(CO)3Cl, were used as probes in compds. contg. 1,3-dimethyllumazine (DML), 1,3-dimethylalloxazine (DMA), 2-pivaloylpterin (PP) and 6-methyl-2-pivaloylpterin (MPP) as biochem. relevant ligands. Evidence from spectroscopy (NMR, IR, UV-visible) in aprotic solvents points in most cases to the O4 and N5 atoms as chelate donors for metal binding. For (DMA)IrIIICp*Cl(PF6) this was substantiated by a crystal structure anal. With PP, however, an Ir(III) compd. with pivaloyl-coordinated metal was obtained. Whereas both the IrIII and Re1 complexes of the good p acceptor ligand DMA can be reduced reversibly and thus studied by (spectro)electrochem. (IR, UV-visible, EPR: ligand-centered 1-electron redn.), the DML system exhibits such behavior only for the IrIII species. The complexes of the 2-pivaloylpterins showed only irreversible redn. on SciFinder(R)
@article{Heilmann.1999,
abstract = {Two organometallic complex fragments with 5d6 configurated metal centers of different character, electrophilic [IrIIICp*Cl]+ and \textgreek{p}-donating [ReI(CO)3Cl], were used as probes in compds. contg. 1,3-dimethyllumazine (DML), 1,3-dimethylalloxazine (DMA), 2-pivaloylpterin (PP) and 6-methyl-2-pivaloylpterin (MPP) as biochem. relevant ligands. Evidence from spectroscopy (NMR, IR, UV-visible) in aprotic solvents points in most cases to the O4 and N5 atoms as chelate donors for metal binding. For [(DMA)IrIIICp*Cl](PF6) this was substantiated by a crystal structure anal. With PP, however, an Ir(III) compd. with pivaloyl-coordinated metal was obtained. Whereas both the IrIII and Re1 complexes of the good \textgreek{p} acceptor ligand DMA can be reduced reversibly and thus studied by (spectro)electrochem. (IR, UV-visible, EPR: ligand-centered 1-electron redn.), the DML system exhibits such behavior only for the IrIII species. The complexes of the 2-pivaloylpterins showed only irreversible redn. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Heilmann, Oliver and Hornung, Fridmann M. and Fiedler, Jan and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/26807a392619458788a19f14c521e2e35/b_schwederski},
doi = {10.1016/S0022-328X(99)00294-6},
interhash = {65d2f2f928547de68a075e47fbc512dc},
intrahash = {6807a392619458788a19f14c521e2e35},
journal = {Journal of Organometallic Chemistry},
keywords = {alloxazine complex complex;ESR complex;electrochem complex;iridium crystal cyclopentadienyl dimethylalloxazine electrochem iridium pivaloylpterin prepn redn redn;rhenium rhenium structure},
number = 1,
pages = {2--10},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Organometallic iridium(III) and rhenium(I) complexes with lumazine, alloxazine and pterin derivatives},
volume = 589,
year = 1999
}