In situ syntheses of trans-spanned octahedral ruthenium complexes. Crystal structures of trans-(Ru(Cl)(trpy){Ph_2PC_6H_4CH_2O(CO)_(CH_2)_4(CO)OCH_2C_6H_4PPh_2})(PF_6) centre dot 0.25 C_6H_5Me centre dot CH_2Cl_2 and trans-(Ru(Cl)(trpy)(PPh_3)_2)(BF_4

摘要

The formation of stable, undistorted octahedral transition metal complexes which contain a trans-spanning bidentate ligand remains a synthetic challenge. The reported complexes are of the type trans-[Ru(Cl)(trpy){Ph_2PC_6H_4CH_2O(CO)Y(CO)OCH_2C_6H_4PPh_2}][PF_6] [where trpy = 2, 2':6', 2"-terpyridine and Y = (CH_2)_3 = C3SPAN, 6; (CH_2)_4 = C4SPAN, 7; or isophthalate = ISPAN, 8] and represent the first examples of trans-spanned transition metal complexes which display little bond angle distortion from octahedral geometry and also contain a bridging linkage which is stable towards oxidation, reduction and hydrolysis. These complexes were characterized by elemental analyses, cyclic voltammetry, conductivity and UV/VIS spectroscopy. COSY, HETCOR and variable temperature (~1H and ~(13)C) NMR spectra of the complexes are consistent with a flexible spanning linkage that does not demonstrate restricted rotation about either the P-C_(ipso) or the Ru-P bonds while the X-ray crystal structure analysis of 7 showed that the spanning linkage is positioned to one side of the meridional chloride.