%0 Journal Article %A Antiñolo, Antonio %A García-Yuste, Santiago %A Otero, Antonio %A Pérez-Flores, Juan C. %A Reguillo-Carmona, Rebeca %A Rodríguez, Ana M. %A Villaseñor, Elena %D 2006 %T Reactivity of a Phosphido-Niobocene Derivative toward CS2 and Alkyl Halides to Give Phosphinodithioformato- and Phosphino-Niobocene Complexes:  X-ray Crystal Structures of [Nb(η5-C5H4SiMe3)21-S-SC(S)(PPh2))(CO)] and [Nb(η5-C5H4SiMe3)2(P(I)Ph2)(CO)]I3 %U https://acs.figshare.com/articles/journal_contribution/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_sup_5_sup_C_sub_5_sub_H_sub_4_sub_SiMe_sub_3_sub_sub_2_sub_sup_1_sup_S_SC_/3236278 %R 10.1021/om051013u.s002 %2 https://ndownloader.figshare.com/files/5070343 %K CH 2 Ph %K latter compound %K Br %K Alkyl Halides %K 2 species %K diphenylphosphinodithioformato ligand %K alkyl halides RX %K CO elimination %K insertion reaction %K niobocene system %K phosphido terminal ligand %K Nb %K C 5 H 4 SiMe 3 %K carbon disulfide %K electrophilic attack %K ICH 2 CH 2 %K CS 2 %K phosphorus atom %K CH 2 CH 2 Ph %X 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)21-S-SC(S)(PPh2))(CO)] (3) and [Nb(η5-C5H4SiMe3)22-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. %I ACS Publications