Preparation of hydride complexes of ruthenium with bidentate phosphite ligands

Hydride complex RuH2(PFFP)(2) (1) [PFFP = (CF3CH2O)(2)PN(CH3)N(CH3)P(OCH2CF3)(2)] was prepared by allowing the compound RuCl4(bpy) center dot H2O (bpy = 1,2-bipyridine) to react first with the phosphite PFFP and then with NaBH4. Chloro-complex RuCl2(PFFP)(2) ( 2) was also prepared, either by reacting RuCl4( bpy) H2O with PFFP and zinc dust or by substituting triphenylphosphine with PFFP in the precursor complex RuCl2(PPh3)(3). Hydride derivative RuH2(POOP)(2)(3) (POOP = Ph2POCH2CH2OPPh2) was prepared by reacting compound RuCl3(AsPh3)(2)(CH3OH) first with the phosphite POOP and then with NaBH4. Depending on experimental conditions, treatment of carbonylated solutions of RuCl3 center dot 3H(2)O with POOP yields either the cis- or trans-RuCl2(CO)(PHPh2)(POOP) (4) derivative. Reaction of both cis- and trans-4 with LiAlH4 in thf affords dihydride complex RuH2(CO)(PHPh2)(POOP) (5). Chloro-complex all trans-RuCl2(CO)(2)(PPh2OMe)(2) (6) was obtained by reacting carbonylated solutions of RuCl3 center dot 3H(2)O in methanol with POOP. Treatment of chloro-complex 6 with NaBH4 in ethanol yielded hydride derivative all-trans-RuH2(CO)(2)(PPh2OMe)(2) (7). The complexes were characterised spectroscopically and the X-ray crystal structures of complexes 1, 3, cis- 4 and 6 were determined. (C) 2007 Elsevier B.V. All rights reserved.