The synthesis of [Cp2ZrH(CH2PPh2)]n, 1, and its chemical behavior toward different organic or organometallic substrates are described. The chemical reduction of the hydride 1 produced a paramagnetic Zr(III) species formulated as [CpZr(eta-2-CH2PPh2)2], and a redistribution reaction from the unstable [Cp2ZrH(CH2PPh2)]- is suggested. The thermolytic experiment of 1 led to the Zr(III) species "Cp2ZrH" and [Cp2Zn(eta-2-CH2PPh2)], and a mechanistic pathway implying the reductive elimination of the phosphine CH3PPh2 is proposed. Indirect evidence comes from the thermolysis of [Cp2ZrD(CH2PPh2)]n and [(C5D5)2ZrD(CH2PPh2)]n or from the reactivity of 1 With PhC=CPh, Cp2Zr(Ph)2, or Cp2Zr(eta-4-butadiene). A Zr(IV)-Zr(II) homodimetallic hydride [Cp2Zr(mu-H)(mu-CH2PPh2)ZrCp2] is postulated as an intermediate in the decomposition scheme of 1.
The synthesis of [Cp2ZrH(CH2PPh2)]n, 1, and its chemical behavior toward different organic or organometallic substrates are described. The chemical reduction of the hydride 1 produced a paramagnetic Zr(III) species formulated as [CpZr(eta-2-CH2PPh2)2], and a redistribution reaction from the unstable [Cp2ZrH(CH2PPh2)]- is suggested. The thermolytic experiment of 1 led to the Zr(III) species "Cp2ZrH" and [Cp2Zn(eta-2-CH2PPh2)], and a mechanistic pathway implying the reductive elimination of the phosphine CH3PPh2 is proposed. Indirect evidence comes from the thermolysis of [Cp2ZrD(CH2PPh2)]n and [(C5D5)2ZrD(CH2PPh2)]n or from the reactivity of 1 With PhC=CPh, Cp2Zr(Ph)2, or Cp2Zr(eta-4-butadiene). A Zr(IV)-Zr(II) homodimetallic hydride [Cp2Zr(mu-H)(mu-CH2PPh2)ZrCp2] is postulated as an intermediate in the decomposition scheme of 1.