Studies on the Reactivity of the Aminophosphino [W 3 S 4 Br 3 (edpp ) 3 ] + (edpp= (2 - aminoethyl) diphenylphosphine) Cluster Cation towards Bases Reveal ing a Non - Passive Role of the Amino Group
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Otros documentos de la autoría: Pino Chamorro, Jose Angel; Beltrán Álvarez, Tomás Francisco; Fernández-Trujillo, M. Jesús; García Basallote, Manuel; Llusar, Rosa; Algarra, Andrés G.
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Título
Studies on the Reactivity of the Aminophosphino [W 3 S 4 Br 3 (edpp ) 3 ] + (edpp= (2 - aminoethyl) diphenylphosphine) Cluster Cation towards Bases Reveal ing a Non - Passive Role of the Amino GroupAutoría
Fecha de publicación
2017-11-24Editor
WileyCita bibliográfica
PINO CHAMORRO, José Ángel; BELTRÁN ÁLVAREZ, Tomás Francisco; FERNÁNDEZ-TRUJILLO, María Jesús; BASALLOTE, Manuel G.; LLUSAR, Rosa; ALGARRA, Andrés G. Studies on the Reactivity of the Aminophosphino [W 3 S 4 Br 3 (edpp ) 3 ] + (edpp= (2 - aminoethyl) diphenylphosphine) Cluster Cation towards Bases Reveal ing a Non - Passive Role of the Amino Group. European Journal of Inorganic Chemistry (2017), issue 43, p. 5006-5014Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.201700641Versión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
Detailed studies using stopped-flow, 31
P{
1
H} NMR, a
nd
ESI
-
MS have been carried on the reaction
of the [W
3
S
4
Br
3
(edpp)
3
]
+
(edpp =
(
2
-
aminoethyl)diphenylphosphine
) ... [+]
Detailed studies using stopped-flow, 31
P{
1
H} NMR, a
nd
ESI
-
MS have been carried on the reaction
of the [W
3
S
4
Br
3
(edpp)
3
]
+
(edpp =
(
2
-
aminoethyl)diphenylphosphine
) cluster with
NaOH and
Et
3
N in acetonitrile. The
study
has allowed identification of h
ydroxo
species during the reactivity studies an
d the development of a
procedure for the
synthesis of the
[W
3
S
4
(OH)
3
(edpp)
3
]
+
cluster in high
yields. This involves the substitution of the coordinated bromides by
OH
-
ligands, and the associated kinetics is several orders of
magnitude faster than that with Cl
-
, F
-
, and SCN
-
anions. The reactivity
with Et
3
N is quite different and essentially leads to the formation of
species resulting from proton abstraction at the NH
2
groups of the
edpp ligands, the amine acting as a base. DFT calculations provide a
rationalization of the experimental findings by showing that Et
3
N
coordination does not occur even in the presence of a vacant
coordination site. Computed pKa values for the
different species
involved in these reactions indicate the possibility of proton exchange
between the NH
2
groups of edpp and Et
3
N, which is confirmed by the
NMR and ESI
-
MS data. The formation of intermediate cluster species
containing the conjugate base o
f edpp has been also found to
facilitate bromide dissociation, thus providing a reaction pathway with
a lower energy barrier that justifies the faster formation of
[W
3
S
4
(OH)
3
(edpp)
3
]
+
with respect to other [W
3
S
4
X
3
(edpp)
3
]
+
(X= Cl, F,
SCN) clusters. [-]
Publicado en
European Journal of Inorganic Chemistry (2017), issue 43Proyecto de investigación
The financial support of the Spanish Ministerio de Economía y Competividad and FEDER funds (Project Nos. CTQ2015 - 65707 - C2 - 2 - P and CTQ2015 - 65207 - P) is gratefully acknowledged.Derechos de acceso
http://rightsstatements.org/vocab/CNE/1.0/
info:eu-repo/semantics/openAccess
info:eu-repo/semantics/openAccess
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