RT info:eu-repo/semantics/article
T1 Polymer [Pd(CH2SO2C6H4Me)2]n, a precursor to remarkably stable Pd organometallics
A1 Pérez Briso, Celeste
A1 Gallego, Ana María
A1 Martín Álvarez, José Miguel
A1 Martínez de Ilarduya Martínez de Ilarduya, Jesús María
A1 Espinet Rubio, Pablo
K1 Polímeros
K1 Compuestos organometálicos
AB A polymer [Pd(CH2SO2C6H4Me)2]n is obtained by thermolysis of cis-[Pd(CH2SO2C6H4Me)2(NCMe)2] to release the MeCN ligands. The corresponding coordination sites are then occupied by weak Pd–O bonds, easier to break than the previous Pd–N bonds. This allows us to produce from the polymer cis complexes containing ligands weaker than NCMe, such as acetone or water. The complexes cis-[Pd(CH2SO2C6H4Me)2{OC(CD3)2}2], cis-[Pd(CH2SO2C6H4Me)2(OH2)2], and cis-[Pd(CH2SO2C6H4Me)2(OH2){OC(CD3)2}], and cyclic dimers [Pd(CH2SO2C6H4Me)2(OH2)]2 with bridging methylsulphone groups are formed. The Pd : PPh3 : OH2 1 : 1 : 1 reaction of the polymer produces cis-[Pd(CH2SO2C6H4Me)2(OH2)(PPh3)], which isomerizes to trans-[Pd(CH2SO2C6H4Me)2(OH2)(PPh3)], with water O-coordinated to Pd and making hydrogen bonds to the two SO2 groups as seen in its X-ray structure. A similar role is played by RNH2 groups in the structures of trans-[Pd(CH2SO2C6H4Me)2(NH3)(PPh3)] and the dimer μ-(N2H4)(trans-[Pd(CH2SO2C6H4Me)2(PPh3)])2. In addition to these interesting intramolecular hydrogen bonding properties provided by the SO2 groups, the structural and 1H NMR data available suggest that the CH2SO2C6H4Me group is an interesting kind of strong alkyl σ donor, with high trans influence, and forms very stable Pd complexes extraordinarily resistant to reductive elimination and to hydrolysis by water at room temperature.
PB Royal Society of Chemistry
SN 1477-9226
YR 2017
FD 2017
LK http://uvadoc.uva.es/handle/10324/28846
UL http://uvadoc.uva.es/handle/10324/28846
LA eng
NO Dalton Transactions, 2017, 46, 25, p. 8083-8090
NO Producción Científica
DS UVaDOC
RD 24-nov-2024