2024-03-28T22:18:35Zhttp://uvadoc.uva.es/oai/requestoai:uvadoc.uva.es:10324/288462021-06-23T11:53:20Zcom_10324_1186com_10324_931com_10324_894col_10324_1404
Polymer [Pd(CH2SO2C6H4Me)2]n, a precursor to remarkably stable Pd organometallics
Pérez Briso, Celeste
Gallego, Ana María
Martín Álvarez, José Miguel
Martínez de Ilarduya Martínez de Ilarduya, Jesús María
Espinet Rubio, Pablo
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.
2018-08-08T23:40:47Z
2018-08-08T23:40:47Z
2018-08-08T23:40:47Z
2017
info:eu-repo/semantics/article
Dalton Transactions, 2017, 46, 25, p. 8083-8090
1477-9226
http://uvadoc.uva.es/handle/10324/28846
http://dx.doi.org/10.1039/c7dt00904f
Dalton Transactions
eng
http://pubs.rsc.org/en/content/articlelanding/2017/dt/c7dt00904f
info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
Attribution-NonCommercial-NoDerivatives 4.0 International
Royal Society of Chemistry