%0 Journal Article 
%A Guillamón, Eva
%A F. Beltrán, Tomás
%A S. Safont, Vicent
%A Castillo González, Carmen Esther
%A García Algarra, Andrés
%A Fernández-Trujillo Rey, María Jesús
%A Pedrajas Gual, Elena
%A Pino Chamorro, Jose Ángel
%A García Basallote, Manuel
%A Llusar, Rosa
%T Bifunctional W/NH Cuboidal Aminophosphino W3S4 Cluster Hydrides: The Puzzling Behaviour behind the Hydridic-Protonic Interplay
%D 2021
%@ 1434-1948
%U http://hdl.handle.net/10498/34315
%X The novel [W3S4H3(edpp)3]+ (edpp = (2-aminoethyl)diphenylphosphine) (1+) cluster hydride with an acidic –NH2 functionality has been synthetized and studied. Its crystal structure shows the characteristic incomplete W3S4 cubane core with the outer positions occupied by the P and N atoms of the edpp ligands. Although no signal due to the hydride ligands is observed in the 1H NMR spectrum, hydride assignment is supported by 1H-15N HSQC techniques, the changes in the 31P{1H} NMR chemical shift, and FT-IR spectra in the W-H region of the deuterated [W3S4D2H(edpp)3]+     (1+-d2) samples. Moreover, all NMR evidences suggest that one of the hydrogen atoms of the NH2 group in 1+ is rapidly exchanging with the hydride. The reaction of 1+ with acids (HCl, HBr and DCl) features complex polyphasic kinetics with zero-order dependence with respect to the acid concentration, being also independent of the solvent nature. This behavior differs from that of their diphosphino analogues, suggesting a different mechanism.
%K Crystal structure
%K Hydride ligands
%K Kinetics
%K N,P ligands
%K Tungsten cluster sulfides
%~ Universidad de Cádiz