RT journal article
T1 Bifunctional W/NH Cuboidal Aminophosphino W3S4 Cluster Hydrides: The Puzzling Behaviour behind the Hydridic-Protonic Interplay
A1 Guillamón, Eva
A1 F. Beltrán, Tomás
A1 S. Safont, Vicent
A1 Castillo González, Carmen Esther
A1 García Algarra, Andrés
A1 Fernández-Trujillo Rey, María Jesús
A1 Pedrajas Gual, Elena
A1 Pino Chamorro, Jose Ángel
A1 García Basallote, Manuel
A1 Llusar, Rosa
A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
A2 Física de la Materia Condensada
K1 Crystal structure
K1 Hydride ligands
K1 Kinetics
K1 N,P ligands
K1 Tungsten cluster sulfides
AB 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.
PB Wiley
SN 1434-1948
YR 2021
FD 2021
LK http://hdl.handle.net/10498/34315
UL http://hdl.handle.net/10498/34315
LA eng
DS Repositorio Institucional de la Universidad de Cádiz
RD 08-nov-2026