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Relevant academic research and scientific papers

Bimetallic complexes III. Synthesis and reactions of c5h4pph2-bridged zirconium-molybdenum and zirconium-tungsten complexes

The synthesis and reactions of bimetallic Zr-Mo and Zr-W complexes with bridging C5H4PPh2 ligands (henceforth abbreviated as Cp′) are described. Reaction of Cp′2ZrCl2 (1) with organolithium or Grignard reagents gives Cp′2ZrR2 (R = Me (3), p-C6H4CH3 (5), CH2SiMe3 (6)) while with A1Me3 the mono-exchange product Cp′2Zr(Cl)Me (2) is formed. Phenyllithium converts 2 into Cp′2Zr(Me)Ph (4). From 1-3 the substitution products [(Cp′2ZrMe)2( μ-O)] (7), Cp′2Zr(SR)2 (R = Me (8a), Ph (8b), CH2C6H4Cl (8c)), Cp′2Zr(Me)OR (R = CH2CF3 (9a), t-Bu (9b)), and Cp′2Zr(Cl)Ot-Bu (10) were obtained. Treatment of [Mo(CO)4(norbornadiene)] with either 2, 4 or 9a gives the bis-Cp′ bridged binuclear tetracarbonyl complexes [Cp′2Zr(Me)(X)Mo(CO)4] (X = Cl (11), Ph (12), OCH2CF3 (13)). Binuclear complexes [Cp′2Zr(X)( μ-Cl)M(CO)3] (X = Me, M = Mo, W (14a,b), X = Ot-Bu, M = Mo (16)) which contain an additional bridging chloride ligand were obtained similarly from [M(CO)3(cycloheptatriene)] and the appropriate zirconium compound. The chloride bridge is readily opened by addition of either PMe3 or t-BuNC producing complexes [Cp′2ZrCl2M(CO)3L] (L = PMe3 (18a,b), t-BuNC (19a,b)) and [Cp′2Zr(Cl)(Me)M(CO)3PMe3] (20a,b; M = Mo (a), W (b)). Exchange of zirconium-bound chloride for organic groups is achieved by treatment of 18a,b or 19a,b with LiR which gives [Cp′2ZrMe2M(CO)3L] (L = PMe3 (21a,b), t-BuNC (22a,b), M = Mo (a), W (b)) as well as [Cp′2ZrR2Mo(CO)3PMe3] (R = Ph (23), Tol (24)). C-C coupling of two nitrile ligands with a Zr-bound methyl group to give a bridging 1,3-diiminato ligand takes place upon reacting Cp′2ZrMe2 (3) with [W(CO)3(NCR)3]. The products [Cp′2Zr( μ-HN-C(R)=CH-C(R)=N)W(CO)3] (R = Ph (25), CH2Ph (26)) were fully characterized by magnetic resonance including 13C-NMR of the doubly labelled derivative 26*. Protonation of 26 using [PhMe2NH]BPh4 gives the corresponding 1,3-diimine complex [Cp′2Zr( μ-HN=C(R)-CH2-C(R)=N)W(CO)3]BPh4 (R = CH2Ph, 27).

Synthesis and crystal struture of the complex cis-1,3-bis(diphenylphosphino)dicyclopentadiene tetracarbonylmolybdenum

The interaction of cis-Mo(CO)4(Ph2PCl)2 with 2 equivalents of (C5H5)Tl in refluxing toluene gives the complex cis-1,3-bis(diphenylphosphino)(dicyclopentadiene(tetracarbonyl)molybdenum in high yield.The compound has been fully characterized by analytical, spectroscopic, and X-ray diffraction methods.A mechanism for the formation of the complex is proposed.