356528-26-2Relevant articles and documents
Synthesis, characterisation and reactivity of ruthenium bis-bifluoride, ruthenium hydride bifluoride and ruthenium hydride fluoride complexes
Jasim,Perutz,Foxon,Walton
, p. 1676 - 1685 (2007/10/03)
Bifluoride complexes, trans-[Ru(depe)2H(FHF)] (1), trans-[Ru(dppe)2H(FHF)] (2), trans-[Ru(dppp)2H(FHF)] (3) and cis-[Ru(PMe3)4(FHF)2] (4) (depe = Et2PCH2CH2PEt2, dppe = Ph2PCH2CH2PPh2, dppp = Ph2PCH2CH2CH2PPh2) were synthesised from the reactions of the corresponding cis-dihydride complexes with NEt3·3HF in THF. The characteristic features of the low temperature NMR spectra of the bifluoride complexes include 19F resonances at ca. δ -300 for the proximal fluorine and ca. δ -165 for the distal fluorine. The acidic protons resonate at ca. δ 13. The value of J(HF) for the distal fluorine lies in the range 300-400 Hz. The bifluoride ligands exhibit characteristic vibrations at ca. 2300 cm-1 and ca. 2430 cm-1 in the IR spectrum. All the complexes exhibit dynamic exchange processes, probably due to dissociation of FHF-. In addition, complex 3 undergoes a ring flipping process that is suppressed at low temperature. The X-ray crystal structure of 3 has been obtained. The bifluoride ligand is disordered over two positions about the inversion centre. The Ru-F distance is 2.351(5) A and the F···F distance is 2.290(8) A, the Ru-F···F angle is 149.7°. The X-ray crystal structure for 4 reveals that the Ru-F distances are 2.149(5) A and 2.150(4) A, the F···F bond lengths are 2.323(8) A and 2.329(8) A, with Ru-F···F angles of 128.5(3)° and 138.4(3)°. The two bifluoride ligands are cis to each other. Reaction of 1 and 3 with [NMe4]F yields trans-[Ru(depe)2(H)F] 5 and trans-[Ru(dppp)2(H)F] 6. Reaction of 2 with Me3SiX (X = N3, OTf) yields trans-[Ru(dppe)2(H)N3] and [Ru(dppe)2(H)]OTf. Reactions with several halo-organic compounds yields trans-[Ru(dppe)2(H)X] (X = Cl, Br and I). The organic products from CH3I, CH3COCl and C6H5COCl were identified as CH3F, CH3COF and C6H5COF respectively.
