Organosulfur derivatives of the metal carbonyls. XIII. Some trifluoromethylthio derivatives of metal carbonyls and cyclopentadienyls

A Re(CO)5Fragment Bonded to a Polyhedral Oligomeric Hydroxysilsesquioxane as a Model which Gives Further Evidence to the Existence of an Unexpected Re(CO)5Surface Species

“…24 This distance is shorter than with four-electron donor bridges of the third period or below (3.8-4.0 Å) but is in agreement with the other Re 2 (CO) 8-n L n (OR) 2 (n ) 1, 2) species known (L ) any noncarbonyl ligand), 25 meaning that the oxo bridge requires a much smaller Re-O-Re angle. 26 The observed stereochemistry around the oxygen bridge is close to a (distorted) trigonal coordination rather than pyramidal as observed for S-bridged dimers 20 (<Re-O-Si> ) 126°; <Re-O-Re> ) 106°; O, Si, and the two Re atoms lie almost on the same plane). Each O 12 Si 8 (c-C 6 H 11 ) 7 group can be regarded as a slightly distorted cube, whose vertexes are occupied by Si atoms (Si‚‚‚Si in the range 3.03-3.17 Å), attached to the µ 2 bridging oxygen along one of its 3-fold axes.…”

“…To our knowledge, 2 is the first example of a μ-oxo-bridged dimer of the type [Re 2 (CO) 8 (μ-OR) 2 ], although related [Re 2 (CO) 8 (μ-SR) 2 ] complexes (R = C 6 F 5 or C 6 H 5 , CF 3 ) are known and species of the type [Re 2 (CO) 8 (μ-OR) 2 ] (R = Ph, H) have been proposed (but never detected) as possible intermediates in the syntheses of [Re 3 (μ 3 -OMe)(μ-OR) 3 (CO) 9 ] - . The structure of 2 has been unambiguously established by X-ray diffraction analysis of crystals grown from CH 2 Cl 2 or n -pentane solutions at 253 K (Figure B).…”

Unexpected substitution reactions of alkoxy-, acyloxy-, and chlorobis(.eta.5-cyclopentadienyl)methyltitanium(IV) complexes with acids

“…Preparation of Bis(it'-cyclopentadienyl)bis(carboxylato)titanium(IV) (8) from 6 and 4: Typical Procedure. A solution of 2.28 g (10 mmol) of bis(i)5-cyclopentadienyl)chloromethyltitanium(IV) (6) and 10 mmol of carboxylic acid 4 in 100 mL of toluene was stirred at room temperature for 24 h, at which time an orange precipitate had formed.…”