Proton transfer in aminocyclopentadienyl ruthenium hydride complexes

José A. Ayllon (1) , Stephen F. Sayers (1) , Sylviane Sabo-Etienne (1) , Bruno Donnadieu (1) , Bruno Chaudret (1) , Eric Clot (2)

1 LCC - Laboratoire de chimie de coordination
2 LSDSMS - Laboratoire de structure et de dynamique des systèmes moléculaires et solides

A new ruthenium hydride complex of the aminocyclopentadienyl ligand (Cp-N)RuH(PPh3)(2) (Cp-N = C5H4CH2CH2NMe2, 1) has been prepared and characterized by X-ray diffraction. Protonation of 1 with excess HPF6 leads to the dicationic derivative [(Cp-NH)RuH2(PPh3)(2)](PF6)(2) (2), in which both the metal and the amino substituent have been protonated. Addition of 1 equiv of HBF4. Et2O to 1 leads to the complex [(Cp-N)Ru(PPh3)(2)](BF4) (3), containing a chelating amino cyclopentadienyl ligand after elimination of Ha However, using (HNEt3)(BPh4) or (HPBu3)(BPh4) as protonating agent, it is possible to form [(Cp-NH)RuH(PPh3)(2)](BPh4) (4), which was isolated as yellow crystals of 4 . H2O upon addition of undistilled methanol and characterized by X-ray crystallographic analysis. A fluxional process exchanging the ammonium proton and the hydride without changing the thermodynamic state of the system could be established by H-1 NMR, and activation energies of 11 kcal.mol(-1) were calculated for 4 . H2O and the product resulting from in situ addition of [HNEt3][BPh4] to 1, whereas an activation energy of 10.1 kcal.mol(-1) was found for the product resulting from in situ addition of [HPBu3][BPh4] to 1. A density functional study (B3PW91) was carried out, and the dihydrogen bond in the model system for 4 was calculated to be 1.545 Angstrom, in excellent agreement with T-1 measurements (1.52 Angstrom). The proposed mechanism for the fluxional process does not involve a proton transfer within the dihydrogen bond.

Mots clés: EFFECTIVE CORE POTENTIALS; MOLECULAR-STRUCTURE; HYDROGEN-BOND; DIHYDROGEN; CRYSTAL; REACTIVITY; CHEMISTRY; EXCHANGE; LIGAND; ATOMS

Domaines: Chimie-Physique [physics.chem-ph]

José A. Ayllon, Stephen F. Sayers, Sylviane Sabo-Etienne, Bruno Donnadieu, Bruno Chaudret, et al.. Proton transfer in aminocyclopentadienyl ruthenium hydride complexes. Organometallics, 1999, 18, pp.3981-3990. ⟨10.1021/om990301l⟩. ⟨hal-00429112⟩