Ansa [1]Trochrocenophanes and Their Related Unstrained 1,1‘-Disubstituted Counterparts: Synthesis and Electronic Structure

The heteroleptic sandwich complex [Cr(η5-C5H5)(η7-C7H7)] (trochrocene) was prepared by
subsequent treatment of CrCl3 with NaCp and Mg in the presence of cycloheptatriene in yields of 40%.
Selective dimetalation employing tBuLi/tmeda (N, N, N‘, N‘-tetramethylethylenediamine) afforded the highly
reactive species [Cr(η5-C5H4Li)(η7-C7H6Li)]·tmeda. An X-ray crystal-structure determination of its thf solvate
revealed a symmetrical, dimeric composition in the solid state, that is, a formula of [Cr(η5-C5H4Li)(η7-C7H6Li)]2·(thf)8, where the C5H4 moieties of both units are connected by two bridging lithium atoms. Addition of
different element dihalides to the dilithio precursor facilitated the isolation of ansa complexes with boron
and germanium in the bridging position. Structural characterization by X-ray diffraction studies on [Cr(η5-C5H4)-BN(SiMe3)2-(η7-C7H6)] and [Cr(η5-C5H4)-GeMe2-(η7-C7H6)] emphasized the strained character with
tilt angles of 23.87(13)° and 15.07(17)°, respectively. In contrast, the isolation of the appropriate
[1]stannatrochrocenophane failed because of the thermal lability of the resulting product. However, the
corresponding 1,1‘-disubstitued derivatives [Cr(η5-C5H4R)(η7-C7H6R)] (R = B(Cl)NiPr2, SiMe3, GeMe3, SnMe3)
were obtained by reverse addition of the dilithio precursor to an excess of the element (di)halide. The
unstrained nature was proven by a crystal structure analysis of the 1,1‘-diborylated species. The electronic
structure of these substituted trochrocene derivatives, as well as of the [2]bora and [n]sila congeners (n =
1, 2), was investigated by means of UV−vis spectroscopy and DFT methods. As a consequence of the
strong electronic influence of the B−N π-system on the LUMOs, the UV−vis studies revealed a
complementary correlation of the lowest energy band maxima as a function of molecular distortion for the
boron containing species on the one hand, and the boron-free compounds on the other hand. These trends
were reproduced fairly well by time dependent DFT calculations.