Bifunctional W/NH Cuboidal Aminophosphino W3S4 Cluster Hydrides: The Puzzling Behaviour behind the Hydridic-Protonic Interplay
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Title
Bifunctional W/NH Cuboidal Aminophosphino W3S4 Cluster Hydrides: The Puzzling Behaviour behind the Hydridic-Protonic InterplayAuthor (s)
Date
2021-09-22Publisher
WileyBibliographic citation
GUILLAMÓN, Eva, et al. Bifunctional W/NH Cuboidal Aminophosphino W3S4 Cluster Hydrides: The Puzzling Behaviour behind the Hydridic‐Protonic Interplay. European Journal of Inorganic Chemistry, 2021, vol. 2021, no 42, p. 4377-4382.Type
info:eu-repo/semantics/articleVersion
info:eu-repo/semantics/submittedVersionSubject
Abstract
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 ... [+]
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. [-]
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Journal of Inorganic Chemistry, 2021, vol. 2021, no 42Funder Name
Spanish Ministerio de Economía y Competitividad | Generalitat Valenciana | Junta de Andalucía | Universitat Jaume I
Project code
PGC2018-094417-B-I00 | PID2019-107006GB-C22 | AICO/2019/192 | FQM-137 | UJI−B2017-44
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