The reaction of (η 5 -i PrC 5 H 4 ) 2 Ti(Me 3 SiC 2 SiMe 3 ) (2) with B(C 6 F 5 ) 3 in toluene at room temperature produces the zwitterionic titanium(III) complex (η 5 -i PrC 5 H 4 )[η 5 -{1,3-i PrC 5 H 3 B-(C 6 F 5 ) 3 }]Ti (3) in which the 3-hydrogen atom of one of the C 5 rings is substituted by a B(C 6 F 5 ) 3 group. The complex is analogous in its structure to the previously described titanium(III) zwitterion Cp[η 5 -C 5 H 4 B(C 6 F 5 ) 3 ]Ti (1) formed in the interaction of B(C 6 F 5 ) 3 with Cp 2 Ti(Me 3 -SiC 2 SiMe 3 ). A characteristic feature of both zwitterionic complexes is the presence of coordinative bonds between the ortho-fluorine atoms of two C 6 F 5 substituents and the positively charged titanium center. Complex 1 is also obtained by the reaction of B(C 6 F 5 ) 3 with Cp 2 Ti(PhC 2 SiMe 3 ). The oxidation of 1 and 3 by air oxygen affords the zwitterionic titanoxanes {Cp[η 5 -C 5 H 4 B(C 6 F 5 ) 3 ]Ti} 2 O (4) and {(η 5 -i PrC 5 H 4 )[(η 5 -{1,3-i PrC 5 H 3 B(C 6 F 5 ) 3 }]Ti} 2 O (5), respectively, which contain two zwitterionic units in the molecule. In each of these units, only one ortho-fluorine atom of a B(C 6 F 5 ) 3 group is involved in the coordination to the titanium atom. Complex 1 readily reacts also with acetone to give the zwitterionic adduct Cp[η 5 -C 5 H 4 B(C 6 F 5 ) 3 ]Ti(Me 2 CO) (6), wherein the molecule of acetone is bonded to the Ti(III) center through the oxygen atom. In this adduct too, only one ortho-fluorine atom of a B(C 6 F 5 ) 3 group is coordinated to the metal.
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