Revealing Coordination Patterns in C<sub>5</sub>-Cyclic Lithium Organics Reent Michel Regine Herbst-Irmer Dietmar Stalke 10.1021/om200471e.s008 https://acs.figshare.com/articles/journal_contribution/Revealing_Coordination_Patterns_in_C_sub_5_sub_Cyclic_Lithium_Organics/2621838 Lithium organics with a C<sub>5</sub> perimeter are the most prominent class of compounds in s-block metal organic chemistry to introduce bulky haptotropic bound substituents in organometallic complexes. In this paper we present some coordination patterns. (η<sup>5</sup>-Cp)Li(PMDETA) (<b>1</b>), (η<sup>5</sup>-Cp)Li(TMEDA) (<b>2</b>), and (η<sup>5</sup>-Cp)Li(DME) (<b>3</b>) reveal the electron-releasing capacity of the donor base: The better the density supply from the base, the longer the Li···Cp<sub>center</sub> distance. The donor base DIGLYME gives the solvent-separated ion pair (SSIP) [(DIGLYME)<sub>2</sub>Li][(η<sup>5</sup>-Cp)<sub>2</sub>Li] (<b>4</b>). The contact ion pair (η<sup>2</sup>-Ind)Li(PMDETA) (<b>5</b>) shows an unprecedented strong C–H···π interaction of a PMDETA methyl group to the center of the C<sub>6</sub> perimeter of an indenyl anion. {(η<sup>5</sup>-Ind)Li(μ-DME)Li(η<sup>5</sup>-Ind)} (<b>6</b>) is a unique DME-bridged dimer, while [(DIGLYME)<sub>2</sub>Li][Ind] (<b>7</b>) crystallizes as a SSIP. 2011-08-22 00:00:00 coordination patterns donor base DIGLYME C 6 perimeter Cp density supply SSIP indenyl anion organometallic complexes PMDETA methyl group Ind Revealing Coordination Patterns C 5 perimeter donor base