Synthesis, crystal structures and some properties of dimethylsilylene-bridged ansa-permethyltitanocene [Ti(IV), (III) and (II)] complexes

Synthesis and Structures of ansa‐Titanocene Complexes with Diatomic Bridging Units for Overall Water Splitting

“…[9] In fact, also in this case, cleavage of the alkyne ligand takes place to give the alkenyl complex 5-alkenyl as a yellow crystalline solid in good yields. [9] In fact, also in this case, cleavage of the alkyne ligand takes place to give the alkenyl complex 5-alkenyl as a yellow crystalline solid in good yields.…”

“…[5] The photoreduction of the complex [Cp* 2 Ti(OH) 2 ] yields the trivalent titanocene complex [Cp* 2 Ti(OH)], thus demonstrating the general feasibility of such compounds to act as model complexes for intermediates in the catalytic cycle of splitting water into its elements (Scheme 1). [8,9] For this reason, the investigation of ansa-titanocenes with different bridging units and thus varying Cp*-Ti-Cp* angles is an attractive target for the elucidation of the reactivity towards small molecules. As a consequence, formation of hydrogen peroxide (from recombination of two OH radicals) is not observed, instead pentamethylcyclopentadi-A C H T U N G T R E N N U N G enA C H T U N G T R E N N U N G ol is found to be the byproduct of the photoreduction.…”

Bis(η5-cyclopentadienyl)titanium(II) in the gas phase:

“…Mass spectra of BTMSA complexes with various titanocenes are characterized by a weak or even absent signal due to a molecular ion and by abundant peaks corresponding to BTMSA and a respective titanocene [19,20,[25][26][27][28][29][30][31]. With all samples of 0 Cp 2 Ti(g 2 -Me 3 SiC 2 SiMe 3 ), ( 0 Cp 2 = g 5 -C 5 H 5 or substituted g 5 -C 5 H 5 ) complexes measured in our laboratory, the abundance of BTMSA +Å ion (m/z 170) relative to 0 Cp 2 Ti +Å and 0 Cp 2 Ti(g 2 -Me 3 SiC 2 SiMe 3 ) +Å ions fluctuated in the course of measurement depending on the direct inlet probe (DIP) as well as on the ion source temperatures.…”

Synthesis and structure of isopropyldimethylsilyl-substituted octamethyltitanocene

“…1-3, respectively, and their important geometric parameters are given in Table 1. Compared with structures of their trimethylsilyl [2,9] or dimethyl(3,3,3-trifluoropropyl)silyl [8] [20], C 5 Me 4 H [7], C 5 Me 4 SiMe 3 [2], C 5 Me 4 (4-fluorophenyl) [21] or [TiMe 2 Si(C 5 Me 4 ) 2 -btmse] [22]. Examination of the cyclopentadienyl ligand structures confirmed the general feature of the silyl-substituted tetramethylcyclopentadienyl ligands that the ring angle at the carbon atom bearing the silicon atom is acute (av.…”

“…Crystallographic data, data collection and structure refinement for compounds 1, 2, 3, 6, and 7 (2) 32.8430 (7) 10.3460 (5) 18.7000 (6) 12.8720(10) b (Å ) 17.0800 (5) 8.8790 (2) 29.2720 (7) 16.0610 (7) 8.5060(4) c (Å ) 22.0430 (5) 21.4310(4) 19.8770 (10) 13.7773(4) 13.8120(10) a (°) 9 0 9 0 9 0 9 0 9 0 b (°) 92.6060 (16) …”