TY - JOUR
T1 - Reactivity of [Ru3(CO)12] towards (EPR2)(E′ PR2′)NH (R = Ph, Me; R′ = Ph; E, E′ = O, S, Se)
T2 - 31P and 77Se NMR spectroscopic characterization and structural analysis of the complexes formed
AU - García-Báez, Efrén V.
AU - Ballinas-López, M. Gabriela
AU - Rosales-Hoz, María J.
AU - Leyva, Marco A.
AU - Haiduc, Ionel
AU - Silvestru, Cristian
N1 - Funding Information:
The present work was part of the Ph.D. Thesis of E.G. at Cinvestav with support of a grant from Conacyt for which E.G. is grateful. We are also grateful to the Consejo Superior de Investigaciones Científicas de España for the award of a licence of the Cambridge Crystallographic Data Base.
PY - 2009/11/16
Y1 - 2009/11/16
N2 - The reaction of [Ru3(CO)12] with the phosphorus chalcogenide ligands (EPR2)(E′ PR2′)NH [E = E′ = S, R = Ph, R′ = Me (L1) and E = E′ = Se, R = R′ = Ph (L2)] produced the complexes [Ru3(μ2-H)(μ3-S){μ2 -S,S,P′-(SPPh2)(PMe2)N}(CO)8] 1, [Ru3(μ2-H)(μ3-S){μ2 -S,S,P′-(SPMe2)(PPh2)N}(CO)8] 2, [Ru3(μ3-S)2{μ2-P,P ′-(Ph2P)(PMe2)NH}(CO)7] 3, [Ru4(μ4-S)2{μ2-P,P ′-(Ph2P)(PMe2)NH}(CO)8(μ 2-CO)] 4, [Ru3(μ2-H)(μ3-Se){μ 2-Se,Se,P′-(SePPh2)(PPh2)N}(CO) 8], 5, [Ru3(μ3-Se)2{μ2-P,P ′-(PPh2)2NH}(CO)7] 6, and [Ru4(μ4-Se)2{μ2-P,P ′-(PPh2)2NH}(CO)8(μ 2-CO)] 7, indicating that cleavage of one of the P{double bond, long}E bonds of the ligand is one of the first steps in the reaction, followed by the cleavage the remaining P{double bond, long}E′ bond. The isostructural tellurium compound, [Ru4(μ4-Te)2{μ2-P,P ′-(PPh2)2NH}(CO)8(μ 2-CO)] 8, was also prepared through the reaction of [Ru3(CO)12] with elemental Te and (PPh2)2NH. When the monothio ligand (SPPh2)(OPPh2)NH (L3) was used, a mononuclear derivative, [Ru{(SPPh2)(OPPh2)N}2(CO)2] 9, was formed suggesting that the presence of an oxygen atom favors the breaking of the metal-metal bonds instead of that of the P{double bond, long}O bond. All these Ru complexes were characterized by spectroscopic methods and the X-ray crystal structures of complexes 1, 2, 3, 6, 8 and 9 were determined, thus allowing comparison between similar compounds containing different donating chalcogen atoms.
AB - The reaction of [Ru3(CO)12] with the phosphorus chalcogenide ligands (EPR2)(E′ PR2′)NH [E = E′ = S, R = Ph, R′ = Me (L1) and E = E′ = Se, R = R′ = Ph (L2)] produced the complexes [Ru3(μ2-H)(μ3-S){μ2 -S,S,P′-(SPPh2)(PMe2)N}(CO)8] 1, [Ru3(μ2-H)(μ3-S){μ2 -S,S,P′-(SPMe2)(PPh2)N}(CO)8] 2, [Ru3(μ3-S)2{μ2-P,P ′-(Ph2P)(PMe2)NH}(CO)7] 3, [Ru4(μ4-S)2{μ2-P,P ′-(Ph2P)(PMe2)NH}(CO)8(μ 2-CO)] 4, [Ru3(μ2-H)(μ3-Se){μ 2-Se,Se,P′-(SePPh2)(PPh2)N}(CO) 8], 5, [Ru3(μ3-Se)2{μ2-P,P ′-(PPh2)2NH}(CO)7] 6, and [Ru4(μ4-Se)2{μ2-P,P ′-(PPh2)2NH}(CO)8(μ 2-CO)] 7, indicating that cleavage of one of the P{double bond, long}E bonds of the ligand is one of the first steps in the reaction, followed by the cleavage the remaining P{double bond, long}E′ bond. The isostructural tellurium compound, [Ru4(μ4-Te)2{μ2-P,P ′-(PPh2)2NH}(CO)8(μ 2-CO)] 8, was also prepared through the reaction of [Ru3(CO)12] with elemental Te and (PPh2)2NH. When the monothio ligand (SPPh2)(OPPh2)NH (L3) was used, a mononuclear derivative, [Ru{(SPPh2)(OPPh2)N}2(CO)2] 9, was formed suggesting that the presence of an oxygen atom favors the breaking of the metal-metal bonds instead of that of the P{double bond, long}O bond. All these Ru complexes were characterized by spectroscopic methods and the X-ray crystal structures of complexes 1, 2, 3, 6, 8 and 9 were determined, thus allowing comparison between similar compounds containing different donating chalcogen atoms.
KW - Clusters
KW - Imidophosphineamine
KW - NMR
KW - Ruthenium
KW - X-ray structure
UR - http://www.scopus.com/inward/record.url?scp=71049119015&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2009.08.026
DO - 10.1016/j.poly.2009.08.026
M3 - Artículo
SN - 0277-5387
VL - 28
SP - 3747
EP - 3754
JO - Polyhedron
JF - Polyhedron
IS - 17
ER -