Diekmann, Mira Bockstiegel, Geert Lützen, Arne Friedemann, Marion Saak, Wolfgang Haase, Detlev Beckhaus, Rüdiger Chiral Bis(η<sup>5</sup>:η<sup>1</sup>-pentafulvene)titanium Complexes The series of bis(pentafulvene)titanium complexes (η<sup>6</sup>-C<sub>5</sub>H<sub>4</sub>CR<sub>2</sub>)<sub>2</sub>Ti (CR<sub>2</sub> = C(<i>p</i>-tol)<sub>2</sub> (<b>3</b>), adamantyl (<b>4</b>)) and their corresponding bis(benzofulvene) derivatives (η<sup>6</sup>-C<sub>9</sub>H<sub>6</sub>CR<sub>2</sub>)<sub>2</sub>Ti (CR<sub>2</sub> = C(<i>p</i>-tol)<sub>2</sub> (<b>7</b>), adamantyl (<b>8</b>)) have been synthesized by reaction of TiCl<sub>3</sub>·3THF with the pentafulvene ligands (2 equiv) and magnesium as reducing agent (1.5 equiv). The bis(fulvene) complexes <b>7</b> and <b>8</b> have been obtained as diastereomerically pure compounds. All complexes have been characterized by spectroscopy and by single-crystal X-ray diffraction. The bonding situation is best described as a π-η<sup>5</sup>:σ-η<sup>1</sup> coordination mode. The bis(fulvene) complex <b>3</b> is approximately <i>C</i><sub>2</sub> symmetric, whereas <b>7</b> crystallizes as a conglomerate in the monoclinic space group <i>P</i>2<sub>1</sub> and one of the enantiomers was identified as a (<i>S</i>,p<i>S</i>,p<i>R</i>) stereoisomer showing <i>C</i><sub>1</sub> symmetry. The adamantyl benzofulvene complex <b>8</b> crystallizes in the monoclinic space group <i>P</i>2<sub>1</sub>/<i>c</i>; both benzofulvene ligands are coordinated as optical antipodes, and a (<i>S</i>,p<i>S</i>,p<i>R</i>)/(<i>R</i>,p<i>R</i>,p<i>S</i>) configuration is found in the solid state. Reaction of <b>3</b> and <b>7</b> with HCl/Et<sub>2</sub>O leads to the corresponding bis(cyclopentadienyl)titanium chlorides (η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>−CHR<sub>2</sub>)<sub>2</sub>TiCl<sub>2</sub> (R = <i>p</i>-tol (<b>9</b>)) and the bis(indenyltitanium) derivative (η<sup>5</sup>-C<sub>9</sub>H<sub>6</sub>−CHR<sub>2</sub>)<sub>2</sub>TiCl<sub>2</sub> (R = <i>p</i>-tol<sub>2</sub> (<b>10</b>)). p S;p R;THF;CHR;bi;C 1 symmetry;tol;space group P 2 1;CR;complex;2 TiCl 2;adamantyl 2006-01-16
    https://acs.figshare.com/articles/dataset/Chiral_Bis_sup_5_sup_sup_1_sup_pentafulvene_titanium_Complexes/3243802
10.1021/om050815m.s005