Insertion Reactions in Ta–H and Ta–Me
Bonds in Complexes Containing Tridentate κ<sup>3</sup>O,S,O-Type
Ligands
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Abstract
A series of new tantalum complexes
containing the κ<sup>3</sup>O,S,O-type alkoxide ligand from
2,2′-thiodiethanol (tdgolH<sub>2</sub>) have been synthesized
and characterized. The complexes [TaCp*Cl<sub>2</sub>{[O(CH<sub>2</sub>)<sub>2</sub>]<sub>2</sub>S-κ<sup>3</sup><i>O</i>,<i>S</i>,<i>O</i>}]
(<b>1</b>) and [TaCp*Me<sub>2</sub>{[O(CH<sub>2</sub>)<sub>2</sub>]<sub>2</sub>S-κ<sup>3</sup><i>O</i>,<i>S</i>,<i>O</i>}] (<b>2</b>) were prepared by reaction
of 2,2′-thiodiethanol with [TaCp*X<sub>4</sub>] (X = Cl, Me).
The tantalum dihydride complex [TaCp*H<sub>2</sub>{[O(CH<sub>2</sub>)<sub>2</sub>]<sub>2</sub>S-κ<sup>3</sup><i>O</i>,<i>S</i>,<i>O</i>}] (<b>3</b>) and its
analogue containing the 2,2′-thiobis(6-<i>tert</i>-octylphenolate) ligand (<b>4</b>) were synthesized by reaction
of the respective dichlorides with 2 equiv of NaBHEt<sub>3</sub>.
In addition, [TaCp*Me(TfO){[O(CH<sub>2</sub>)<sub>2</sub>]<sub>2</sub>S-κ<sup>3</sup><i>O</i>,<i>S</i>,<i>O</i>}] (<b>5</b>) and [TaCp*(TfO)<sub>2</sub>{[O(CH<sub>2</sub>)<sub>2</sub>]<sub>2</sub>S-κ<sup>3</sup><i>O</i>,<i>S</i>,<i>O</i>}] (<b>6</b>; TfO = F<sub>3</sub>COSO<sub>2</sub><sup>–</sup>) were synthesized by reaction
of <b>2</b> with 1 and 2 equiv of triflic acid, respectively.
The reactivity of this family of complexes with nucleophiles was also
studied and, as a result, three azatantalacyclopropane complexes (<b>7</b>–<b>9</b>) and the carbene [TaCp*{C(Me)N(H)xylyl-κ<sup>1</sup>C}(OH){[O(CH<sub>2</sub>)<sub>2</sub>]<sub>2</sub>S-κ<sup>3</sup><i>O</i>,<i>S</i>,<i>O</i>}]
(<b>10</b>) were characterized. The single-crystal structures
of <b>1</b> and <b>6</b> were determined by X-ray diffraction
methods
