A clash of cultures: metal carbonyl functionalized Werner complexes

Reactions of [Fe(1)(2)][PF6](2) (1 =4'-diphenylphosphino-2,2':6',2 "-terpyridine) with [M'(CO)(5)(THF)] (M'=Mo or W) yield [Fe{(mu-1)M'(Co)(5)}(2)][PF6](2). Treatment of [Ru(Cltpy)(2)][PF6](2) (Cltpy = 4'-chloro-2,2':6',2 "-terpyridine) with the [Ph2P](-) anion gives [Ru(1)(2)][PF6](2) which functions as a nucleophile in reactions with [M'(CO)(5)(THF)] (M'=Mo or W) to yield [Ru{(mu-1)M'(CO)(5)}(2)][PF6](2). The bisphosphines [M(1)(2)](2+)(M = Fe or Ru) can be functionalized with triosmium carbonyl clusters by treatment with [Os-3(CO)(11)(NCMe)]. AU new products have been characterized by H-1-, P-31-NMR and IR spectroscopies and mass spectrometry, and the electrochemical properties of the iron(II) complexes have been investigated. (C) 1999 Elsevier Science S.A. All rights reserved.