%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)2(κ1-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)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.
%I ACS Publications