Organometallic rhodium(III) and -(I) complexes with 1,3-dimethyllumazine (DML). The crystal structure of (h2-(O4,N5)-DML)(h5-C5Me5)ClRh(PF6)
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Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences 49 (11): 1554--1560 (1994)

The crystal structure detn. of the new Rh(III)-complex (DML)(C5Me5)ClRh(PF6), (I) DML = 1,3-dimethyllumazine, reveals O4,N5 coordination of the metal to DML with not very different bond lengths of 213.0(2) pm (Rh-N) and 219.2(2) pm (Rh-O). This result stands in contrast to the previously reported structure of a cationic dihydrobiopterin bound to Mo(O)Cl3- which exhibited a very unsym. chelate arrangement. Chem. and electrochem. two-electron redn. of the Rh(III) complex led to a very labile Rh(I) species (DML)(C5Me5)Rh which is distinguished by an intense charge transfer band in the visible range. The results confirm the characterization of DML as a weak s donor/p acceptor ligand with a rather low-lying p* orbital. on SciFinder(R)
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