0000000000131955
AUTHOR
Cyril Poulard
Formation and Reactivity of a Tantalocene Trihydride Containing an Aminoethyl‐Functionalised Ligand
The complex [Cp*{C5H4(CH2CH2NMe2)}TaCl2] (1) was synthesised by reaction of the lithium salt LiC5H4(CH2CH2NMe2) with the tantalum compound [Cp*TaCl3(PMe3)]. Reduction of 1 with NaAl(H)2(OCH2CH2OMe)2 leads to the trihydride derivative [Cp*{C5H4(CH2CH2NMe2)}TaH3] (2). The oxidation of 2 in THF with ferrocenium ion leads to a cationic dihydride intermediate [Cp*{C5H4(CH2CH2NMe2)}TaH2]PF6 (3) with an intramolecular stabilization by the aminoethyl side-chain of the cyclopentadienyl ligand. The hemilabile character of the functionalised cyclopentadienyl ligand was checked by treating 3 with electron-donating ligands (e.g. phosphanes, sulfides, anions); in all cases, no displacement of the amino g…
Tantalocene complexes as bidentate métalloligands: (C5Me5)(C5H4X)Ta(H2)(PPh2) (C5Me5) (C5H4X)Ta(CO) (PPh2) (X = PPh2, CH2CH2NMe2)
Abstract The synthesis of new bidentate metalloligands derived from tantalocene (C5Me5)(C5H4X)Ta(H2)(PPh2) (X = PPh2, 2P; X = CH2CH2NMe22N) and (C5Me5)(C5H4X)Ta(CO)(PPh2) 4(P,N) is described. When opposed to chromium unsaturated fragments the phosphino functionalised complexes 2P and 4P act as chelating bidentate ligands affording Ta(V) (C5Me5)(C5H4PPh2)Ta(CH2) (μ-PPh2)Cr(CO)4 or Ta(III) (C5Me5)(C5H4PPh2)Ta(CO)(μ-PPh2)Cr(CO)4 bimetallic complexes. The same reaction carried out starting from 2N gives rise to a μ-phosphido, μ-hydrido dibridged complex Cp*(C5H4CH2CH2NMe2)TaH(μ-H)(μ-PPh2)Cr(CO)4.