Syntheses, Structures, and Bonding of Cp<sub>2</sub>M(ER)<sub>2</sub> Compounds (Cp = C<sub>5</sub>H<sub>5</sub>; M = Ti, Zr; E = Ga, In; R = C<sub>6</sub>H<sub>3</sub>-2,6-(2,4,6-<i>i</i>-Pr<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>)
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Sodium or magnesium metal reduction of Cp2MCl2 (Cp = C5H5; M = Zr, Ti) with RECl2 (E = Ga, In; R = C6H3-2,6-(2,4,6-i-Pr3C6H2)2) affords heteronuclear organometallic compounds, Cp2M(ER)2, with new types of group 4−group 13 M−E bonds (Zr−Ga (1), Ti−Ga (2), Zr−In (3), Ti−In (4)). These compounds have been characterized by elemental analyses, 1H and 13C NMR spectroscopy, and single-crystal X-ray diffraction analyses. The structures of 1−4 have V-shaped E−M−E trimetallic linkages with quite short M−E bonds (Zr−Ga, 2.6350(8) Å; Ti−Ga, 2.4921(7) Å; Zr−In, 2.7916(5) Å; Ti−In, 2.6685(8) Å). The transition metal (M = Zr, Ti) centers adopt a pseudo-tetrahedral coordination geometry, while the main group metal (E = Ga, In) atoms reside in a two-coordinate, almost linear environment. Density functional theory (DFT) computations on the model compounds Cp2M(EPh)2 (1Ph−4Ph) suggest significant π-back-bonding from the group 4 metals (Zr, Ti) to the group 13 metals (Ga, In) in these compounds.
