Summary
Diazadienes (DAD) (RN=CR′CR′=NR with R′=H or Me and R=n-,i- ort-alkyl, aryl oro,o′-substituted aryl) easily form the thermally inert title compounds [(DAD)-Ru(CO)2I2] (2). Their stereochemistry is unambiguously derived from1H-n.m.r. and i.r. data. One of the complexes (2h) cocrystallizes with the free diazadiene (1h) in a 1∶1 molar ratio. An x-ray diffraction study, which allows a comparison of the free and bound diazadiene. was performed with the monoclinic crystal and gave the following cell parameters: space group C 2/c, a=2237.0(5), b=1017.4(3) and c=1824.9(4) pm, β=105.13(2)°, Z=4. From 2781 observed reflections 293 parameters were refined, leading to a final R-value of 0.0346 (Rw=0.0340). The tilting of thep-tolyl group is a consequence of an intra-ligand repulsion R/R′, the R-conformation being almost equal in the (E,E,E)-shaped molecule (1h) (68°) and the (E,Z,E)-chelate in (2h) (72°). Complexes (2) are photolabile (with loss of CO), and on reduction they lose iodide, thus offering selective ways for the exchange of π-acceptor or σ-donor ligands for precatalyst formation.
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For Part IV see Ref. 1, Part III see Ref. 17; Part II and I, seeTransition Met. Chem., 7, 154 (1982) and6, 185 (1982), respectively.
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Dieck, H.t., Kollvitz, W., Kleinwächter, I. et al. Ruthenium complexes with diazadienes, Part V(1).Cis-Dicarbonyl-1,4-diaza-1,3-diene-trans-diiodoruthenium Complexes; synthesis, properties and the crystal structure of [(DAD)Ru(CO)2I2] · DAD (DAD=p-tolyl-N=CMe-CMe=N-p-tolyl). Transition Met Chem 11, 361–366 (1986). https://doi.org/10.1007/BF01225982
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DOI: https://doi.org/10.1007/BF01225982