Abstract
The dimolybdenum(II) complexes [Mo 2(monp) 4] ( 1) and [Mo 2(msnp) 4] ( 2) (Hmonp = 7-methyl-1,8-naphthyridin-2-one, Hmsnp = 7-methyl-1,8-naphthyridin-2-thione) were prepared by reaction of Mo(CO) 6 with the appropriate ligand in diglyme at 190 °C and their structures established by X-ray structural analysis. Four monoanionic ligands bridge the quadrupole MoMo bonds in 1 and 2 and display respectively 1κ 1 N:2κ 1 O and 1κ 1 N:2κ 1 S coordination modes, trans-MoX 2Y 2 geometries are observed for the individual molybdenum atoms leading to steric crowding of the mutually trans-sited ligands in 2, which is alleviated by a twisting distortion of these ligands with an average torsion angle of 8.0°. Respective MoMo distances of 2.090(4) and 2.131(2) are observed in 1 and 2. The solid-state reaction of Ru 2(OAc) 4Cl with Hmonp at 190 °C leads to the formation of [Ru 2(monp) 4] in which the trans-sited ligands display a 1κ 1 N:2κ 1 N′ coordination pattern. An average twist of 17.7° from the eclipsed conformation is observed which reduces steric repulsions between neighbouring substituents of mutually cis monoanionic ligands. The RuRu bond length of 2.258(2) Å and the magnetic moment of 2.51 BM at 293 K are in accordance with a σ 2π 4δ 2π *2δ *2 electronic configuration.
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