Influence of the Ligand Alkyl Chain Length on the Solubility, Aqueous Speciation, and Kinetics of Substitution Reactions of Water-Soluble M3S4 (M = Mo, W) Clusters Bearing Hydroxyalkyl Diphosphines
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http://dx.doi.org/10.1021/ic400897y |
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Títol
Influence of the Ligand Alkyl Chain Length on the Solubility, Aqueous Speciation, and Kinetics of Substitution Reactions of Water-Soluble M3S4 (M = Mo, W) Clusters Bearing Hydroxyalkyl DiphosphinesAutoria
Data de publicació
2013Editor
American Chemical SocietyISSN
0020-1669; 1520-510XCita bibliogràfica
Inorg. Chem., 2013, 52 (15), pp 8713–8722Tipus de document
info:eu-repo/semantics/articleVersió de l'editorial
http://pubs.acs.org/doi/abs/10.1021/ic400897yVersió
info:eu-repo/semantics/publishedVersionParaules clau / Matèries
Resum
Water-soluble [M3S4X3(dhbupe)3]+ diphosphino complexes
(dhbupe = 1,2-bis(bis(hydroxybutyl)phosphino)ethane), 1+ (M = Mo, X = Cl)
and 2+ (M = W; X = Br), have been synthesized by extending the procedure used
for the ... [+]
Water-soluble [M3S4X3(dhbupe)3]+ diphosphino complexes
(dhbupe = 1,2-bis(bis(hydroxybutyl)phosphino)ethane), 1+ (M = Mo, X = Cl)
and 2+ (M = W; X = Br), have been synthesized by extending the procedure used
for the preparation of their hydroxypropyl analogues by reaction of the
M3S4(PPh3)3X4(solvent)x molecular clusters with the corresponding 1,2-bis-
(bishydroxyalkyl)diphosphine. The solid state structure of the
[M3S4X3(dhbupe)3]+ cation possesses a C3 symmetry with a cuboidal M3S4 unit,
and the outer positions are occupied by one halogen and two phosphorus atoms of
the diphosphine ligand. At a basic pH, the halide ligands are substituted by
hydroxo groups to afford the corresponding [Mo3S4(OH)3(dhbupe)3]+ (1OH+
)
and [W3S4(OH)3(dhbupe)3]
+ (2OH+
) complexes. This behavior is similar to that
found in 1,2-bis(bis(hydroxymethyl)phosphino)ethane (dhmpe) complexes and
differs from that observed for 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe) derivatives. In the latter case, an
alkylhydroxo group of the functionalized diphosphine replaces the chlorine ligands to afford Mo3S4 complexes in which the
deprotonated dhprpe acts in a tridentate fashion. Detailed studies based on stopped-flow, 31P{1
H} NMR, and electrospray
ionization mass spectrometry techniques have been carried out in order to understand the solution behavior and kinetics of
interconversion between the different species formed in solution: 1 and 1OH+ or 2 and 2OH+
. On the basis of the kinetic results, a
mechanism with two parallel reaction pathways involving water and OH− attacks is proposed for the formal substitution of
halides by hydroxo ligands. On the other hand, reaction of the hydroxo clusters with HX acids occurs with protonation of the
OH− ligands followed by substitution of coordinated water by X−. [-]
Publicat a
Inorganic Chemistry, 2013, vol. 52, no 15Drets d'accés
http://rightsstatements.org/vocab/CNE/1.0/
info:eu-repo/semantics/restrictedAccess
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