Reactivity of a Phosphido-Niobocene Derivative toward CS<sub>2</sub> and Alkyl Halides to Give Phosphinodithioformato- and Phosphino-Niobocene Complexes: X-ray Crystal Structures of [Nb(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>SiMe<sub>3</sub>)<sub>2</sub>(κ<sup>1</sup>-S-SC(S)(PPh<sub>2</sub>))(CO)] and [Nb(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>SiMe<sub>3</sub>)<sub>2</sub>(P(I)Ph<sub>2</sub>)(CO)]I<sub>3</sub>
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The reaction of the niobocene complex [Nb(η5-C5H4SiMe3)2(PHPh2)(CO)]Cl (1) with NaOH yielded the corresponding phosphidoniobocene derivative [Nb(η5-C5H4SiMe3)2(PPh2)(CO)] (2) by deprotonation of the P−H bond. The subsequent insertion reaction of carbon disulfide into the Nb−P bond yielded the first examples of a diphenylphosphinodithioformato ligand coordinated to the niobocene system by giving [Nb(η5-C5H4SiMe3)2(κ1-S-SC(S)(PPh2))(CO)] (3) and [Nb(η5-C5H4SiMe3)2(κ2-S,S-SC(S)(PPh2))] (4); the latter compound can also be prepared by the corresponding CO elimination of 3. The cationic d2 species [Nb(η5-C5H4SiMe3)2(PRPh2)(CO)]X (R = Me, X = I (5); CH2Ph, X = Br (6); CH2CH2Ph, X = Br (7)) were prepared by the reaction of alkyl halides RX (R = Me, X = I; CH2Ph, X = Br; CH2CH2Ph, X = Br) with 2 by electrophilic attack on the phosphorus atom present in the phosphido terminal ligand. In the same way, the reaction of 2 with ICH2CH2I yielded the complex [Nb(η5-C5H4SiMe3)2(P(I)Ph2)(CO)]I3 (8). The molecular structures of 3 and 8 were determined by single-crystal X-ray diffraction studies.
