The synthesis, reactivity and modelling studies of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2]: Crystal and molecular structures of [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2] · 3.5CHCl3 and [Ru(NCtBu)(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2][BF4] · 2CHCl3

Treatment of [RuHCl(CO)(PPh3)3] with Hg(C6H4-2-CHO)2 in refluxing toluene gives [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2] 1 in good yield. Treatment of 1 with a stoichiometric amount of Ag[BF4] in CH2Cl2/acetone (1:1) followed by either NCMe, tBuCN or tBuNC to give [Ru(L)(CO)(η2-C,O-C6H4-2-CHO)(PPh3)2][BF4] 2–4 in excellent yields. All of the compounds 1–4 have been characterized by microanalysis, 1H, 13C–{1H} and 31P–{1H} NMR spectroscopy. In addition compounds 1 and 3 have been characterized by single crystal X-ray diffraction studies and the cycloruthenated aldehyde Cdouble bond; length as m-dashO bond length noticeably increases in the cationic system. The complexes [RuCl(CO)(η2-C,O-C6H4-2-CHO)(PH3)2] 1a, [Ru(NCCH3)(CO)(η2-C,O-C6H4-2CHO)(PH3)2] 3a, [Ru(CNCH3)(CO)(η2-C,O-C6H4-2CHO)(PH3)2] 4a [RuCl2{Odouble bond; length as m-dashC(H)Me}(CO)(PH3)2] Xa and [RuCl2{Odouble bond; length as m-dashC(H)HCHdouble bond; length as m-dashCH2}(CO)(PH3)2] XIa have also been modelled using DFT calculations (B3LYP LanL2DZ) and the minimized structures are qualitatively in good agreement with experimentally determined structures. In all cases the calculated Ru–L distances were longer than those observed by experiment, the trend of Ru–C(metalated) did not model the crystallographically observed data and some disparity between the experimental and calculated Cdouble bond; length as m-dashO bond length of the coordinated aldehyde is apparent.