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Structurally characterized acylruthenium organometallics bearing a pendant aldehyde function

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Abstract

By reacting [Ru(RL1)(PPh3)2(CO)Cl], (1) (R = C6H4Me, Et) with an excess of CNBut in the presence of NH4PF6, organometallics of the type [Ru(RL2)(PPh3)2(CNBut)2]PF6, (2) have been isolated in excellent yield [RL1 = C6H2O-2-CHNHR(p)-3-Me-5, RL2 = C6H2(CO)-O-2-CHNHR(p)-3-Me-5]. These organometallics, on controlled hydrolysis, produce [Ru(L3)(PPh3)2(CNBut)2], (3) in very good yield (L3 = C6H2(CO)-O-CHO-3-Me-5). In both ([2(C6H4Me)] · 2H2O) and ([3] · 2CH2Cl2) the two phosphine ligands lie in trans positions. In ([2(C6H4Me)] · 2H2O) the Ru(C6H4MeL2) fragment, excluding the pendant tolyl ring, is a near perfect plane (mean dev ~ 0.02Å) which makes a dihedral angle of 5.2° with the tolyl plane. The acyl chelate ring in ([2(C6H4Me)] · 2H2O) is excellently planar with a mean deviation of 0.006°. In ([3] · 2CH2Cl2) the Ru(L3) fragment defines a crystallographic plane of symmetry, the coordinates of the atom being of the type x, 1/4z. The complex ([2C6H4Me)] · 2H2O) displays N–HȮFO (iminium-phenolato) hydrogen bonding while in ([3] · 2CH2Cl2) C–H...O hydrogen bonding is present. Characteristic spectral data (u.v.–vis, i.r. and 1H n.m.r.) of the complexes are reported. A notable feature is that an allowed band near 500 nm due to the t2g → π*(azomethine) charge transfer transition, which is diagnostic of the coordinated iminium-phenolato function, is present in (3) but this band is absent in the aldehydic acyl complex (2). In the 1H n.m.r. spectrum the N+–H signal in (2) (near 13.5 ppm) is split into a doublet due to transcoupling with the azomethine proton. The aldehydic proton of (3) resonates as a sharp singlet near 10 ppm. In CH2Cl2 solution (2) and (3) display quasireversible a RuIII/RuIIcyclic voltammetric response with E1/2 near 0.9 and 0.5 V versuss.c.e. The conversion (2) → (3) is accompanied by the nucleophilic attack of water. The complex (3) is also obtained directly from (1) by reaction with CNBut in the presence of H2O. The aldehyde function in (3) is deactivated by the existing acyl moiety; as a result further decarbonylation does not take place.

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  1. Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, 700 032, India

    Bikash K. Panda

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Panda, B.K. Structurally characterized acylruthenium organometallics bearing a pendant aldehyde function. Transition Met Chem 30, 488–495 (2005). https://doi.org/10.1007/s11243-004-6970-7

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  • DOI: https://doi.org/10.1007/s11243-004-6970-7

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