Abstract
The dirhodium(I) complex cis-[Rh 2(mphonp) 2(CO) 4] ( 1) was prepared by reaction of 5-methyl-7-phenyl-1,8-naphthyridin-2-one (Hmphonp) with [[RhCl(CO) 2} 2] in methanol in the presence of base (NaOMe). The mphonp − ligands adopt a head-tail orientation relative to one another and bridge the Rh(I) atoms in the O2,N1 coordination mode. Treatment of RhCl 3·3H 2O with mphonp − in methanol affords the dirhodium(II) complex [Rh 2(mphonp) 4] ( 2) in which cyclometalation leads to a novel chelating N8,C72 mode by two of the naphthyridine ligands. The Rh(II) atoms are bridged by the remaining mphonp − ligands with the O2,N1 coordination pattern being supplemented by N 8 as an axial donor atom. This mode requires a pronounced tilting of the bridging ligands towards the RhRh axis leading to very long Rh-O2 distances (av. 2.30(2) Å and wide RhN1C2 angles (av. 133(2)°). The RhRh distances are 2.883(4) and 2.566(3) Å in complexes 1 and 2, respectively (X-ray analyses).
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