The synthesis, reactivity and modelling studies of [RuCl(CO)(eta(2)-C,O-C6H4-2-CHO)(PPh3)(2)]: Crystal and molecular structures of [RuCl(CO)(eta(2)-C,O-C6H4-2-CHO)(PPh3)(2)]center dot 3.5CHCl(3) and [Ru((NCBu)-Bu-t)(CO)(eta(2)-C,O-C6H4-2-CHO)(PPh3)(2

摘要

Treatment of [RuHCl(CO)(PPh3)3] with Hg(C6H4-2-CHO)(2) in refluxing toluene gives [RuCl(CO)(eta 2-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, (BuCN)-Bu-t or (BuNC)-Bu-t to give [Ru(L)(CO)(eta(2)-C, O-C6H4-2-CHO)(PPh3)(2)][BF4] 2-4 in excellent yields. All of the compounds 1-4 have been characterized by microanalysis, H-1, C-13-{H-1} and P-31-{H-1} NMR spectroscopy. In addition compounds 1 and 3 have been characterized by single crystal X-ray diffraction studies and the cycloruthenated aldehyde C=O bond length noticeably increases in the cationic system. The complexes [RuCl(CO)(eta(2)-C, O-C6H4-2-CHO)(PH3)(2)] 1a, [Ru(NCCH3)(CO)(eta(2)-c, O-C6H4-2CHO)(PH3)(2)] 3a, [Ru(CNCH3)(CO)(eta(2)- CO-C6H4-2CHO)(PH3)(2)] 4a [RuCl2{O=C(H)Me)(CO)(PH3)(2)] Xa and [RuCl2(O=C(H)HCH=CH2)(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 C=O bond length of the coordinated aldehyde is apparent. (C) 2007 Elsevier B.V. All rights reserved.