Studies of the 24-Electron <i>n</i><i>ido</i>-5-Vertex Clusters [M(η<sup>4</sup>-P<sub>2</sub>C<sub>2</sub>Bu<sup>t</sup><sub>2</sub>)] (M = Ge, Pb, Sn): Synthesis and Characterization of [M(η<sup>4</sup>-P<sub>2</sub>C<sub>2</sub>Bu<sup>t</sup><sub>2</sub>)] (M = Ge, Pb), [Sn(η<sup>4</sup>-P<sub>2</sub>C<sub>2</sub>Bu<sup>t</sup><sub>2</sub>){W(CO)<sub>5</sub>}<i><sub>n</sub></i>] (<i>n</i> = 1, 2), and [I<sub>2</sub>GeP<sub>2</sub>C<sub>2</sub>Bu<sup>t</sup><sub>2</sub>] and the Mössbauer Spectrum of [Sn(η<sup>4</sup>-P<sub>2</sub>C<sub>2</sub>Bu<sup>t</sup><sub>2</sub>)]
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The group 14 1,3-diphosphacyclobutadienyl complexes [M(η4-P2C2But2)] (M = Ge, Pb) have been synthesized by the reaction of [Zr(η5-C5H5)2(PCBut)2] with GeCl2·(dioxane) or PbI2 and fully characterized by multinuclear NMR spectroscopy and single-crystal X-ray diffraction studies. Structurally they can be viewed as 24-electron nido-5-vertex clusters. The significant solvent dependence of the 207Pb chemical shift of [Pb(η4-P2C2But2)] suggests the possibility of formation of an adduct with Lewis bases. The oxidative addition of [Ge(η4-P2C2But2)] with I2 has been studied as well as the reactivity of the previously reported tin analogue [Sn(η4-P2C2But2)] with [W(CO)5(THF)] in which it coordinates via its P lone pairs. The Mössbauer spectrum of [Sn(η4-P2C2But2)] is reported and shows an isomer shift consistent with it being an organo tin(II) complex.
