Thermodynamic and spectroscopic studies on the complexation of silver(I) by mixed phosphorus–nitrogen ligands in dimethyl sulfoxide and propylene carbonate

Zotto, Alessandro Del; Bernardo, Plinio Dí; Tolazzi, Marilena; Zanonato, Pier Luigi

doi:10.1039/a807556e

Cited by 9 publications

(6 citation statements)

References 47 publications

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“…For DIEN in PC, in addition to AgL and AgL 2 , two polynuclear, Ag 2 L and Ag 3 L 2 , species were also detected, whereas no evidence of a better fit of the data was attained considering the additional presence of Ag 2 L 2 complexes, as previously observed with some other methylenic and ethylenic P-N donors in PC [26]. Noteworthy, Ag 3 L 2 species were also found in PC in the case of some more complex diaza ligands [52].…”

Section: Resultssupporting

confidence: 50%

“…The ligands (Aldrich, >98%) were purified by fractional distillation. DMF and PC (Fluka > 99%) and the background salt NEt 4 ClO 4, used to maintain the required 0.1 M ionic strength were purified according to the described procedures [26,43].…”

Section: Methodsmentioning

confidence: 99%

“…On the basis of thermodynamic data, it can be reasonably supposed that both EN and DIEN behave as bi-and-tridentate in the first complexation step. To support this hypothesis and in absence of a direct possible comparison with a monodentate amine, a comparison with data for the complexation with triphenylphosphine (PPh 3 ) in PC can be done [26].…”

Section: Pcmentioning

confidence: 99%

“…All these studies are of great importance to understand or predict the role of metal ions in biological systems [14] and medicine, where for instance, an accurate description of the thermodynamics of complex formation is of capital importance in the design either of metal sequestering drugs [15,16] and diagnostic agents [17][18][19]. Also interesting structure-stability relationships have been derived when complexes with N-donor ligands are employed as smallmolecule carriers [9,10,12,[20][21][22][23][24] or in homogeneous catalysis when N-N, N-P or N-S chelating ligands were concerned [25,26].…”

Section: Introductionmentioning

confidence: 99%

“…Many thermodynamic studies have been carried out for the coordination of Ag(I), Co(II), Cd (II) and block-f ions with polydentate amines, mostly in dimethylsulfoxide (DMSO) [5,7,10,12,13,[22][23][24]26,[28][29][30][31][32][33][34][35] and acetonitrile (AN) [36][37][38][39][40]. A considerable number of different ligand structures have been studied in these works and the results showed that the strength and nature of the complexes formed were largely influenced by ligands structures and donor-atom basicity and steric properties.…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamics of complex formation of silver(I) with N-donor ligands in non-aqueous solvents

Melchior

Tolazzi

Polese

et al. 2017

J Therm Anal Calorim

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The results of a potentiometric and calorimetric study on the complexation reactions of neutral N donor ligands with silver(I) in propylenecarbonate (PC) and dimethylformamide (DMF) are reported. The ligands concerned in DMF are butylamine (n-but), 1,2-diaminoethane (EN), bis(2aminoethyl)amine (DIEN) and N,N'-bis(2-aminoethyl)ethane-1,2-diamine (TRIEN) whereas in PC results are provided for EN and DIEN, because of side reactions occurring for n-but and TRIEN. The data are compared to those previously reported in dimethylsulfoxide (DMSO), acetonitrile (AN) and water, solvent media which present quite different dielectric constants (ε) and donor numbers (Dn). The trend of stabilities of the mononuclear AgL and AgL 2 formed is discussed in term of different cation and amines solvation in the different solvents. TRIEN can form bimetallic species in DMF, but not in DMSO. Given the lower ε value for DMF than for DMSO, Ag 2 TRIEN formation is evidently more influenced by the lower solvation of Ag(I) ion in DMF, rather than by difference in dielectric constants of these two solvents. In PC in addition to mononuclear complexes of higher stability with respect to the former solvents, also polynuclear Ag 2 L and Ag 3 L 2 species are found.

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Section: Resultssupporting

confidence: 50%

Section: Methodsmentioning

confidence: 99%

Section: Pcmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermodynamics of complex formation of silver(I) with N-donor ligands in non-aqueous solvents

Melchior

Tolazzi

Polese

et al. 2017

J Therm Anal Calorim

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Ring Closure Kinetics of Bidentate Hemilabile P,N and P,S Ligands on a Platinum(II) Complex

Romeo

Scolaro

Plutino

et al. 2002

Eur. J. Inorg. Chem.

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Complexes of the type cis-[PtPh 2 (CO)(η 1 -P−N)] and cis-[PtPh 2 (CO)(η 1 -P−S)], where bidentate phosphorus−nitrogen and phosphorus−sulfur ligands are bound to the metal centre in a monodentate fashion [P−N = Ph 2 PC 5 H 4 N (Ph 2 PPy), Ph 2 P(CH 2 ) 2 C 5 H 4 N (ppye), Ph 2 P(o-C 6 H 4 )NMe 2 (PNMe 2 ), Ph 2 P(CH 2 ) n NMe 2 (n = 2, 3, i.e., peNMe 2 and ppNMe 2 ) and P−S = Ph 2 P(CH 2 ) 2 SEt (P−SEt), Ph 2 P(CH 2 ) n SPh (n = 1, 2, i.e., P−CH 2 SPh and P−SPh)], were prepared in situ by reaction of the hybrid ligands with cis-[PtPh 2 (CO)(SEt 2 )]. In each case, the first observed process was the fast substitution of diethyl sulfide by the phosphanyl group leading to the monosubstituted ring-open cis-[PtPh 2 (CO)(η 1 -P−X)] (X = N or S) complexes, which were characterised in solution by 1 H and 31 P{ 1 H} NMR spectroscopy. These initially formed species undergo a slow ring closure process with extrusion of carbon monoxide and formation of the chelate [PtPh 2 (P−X)] products, except in the case of the short-bite Ph 2 PPy and P−CH 2 SPh ligands and of ppNMe 2 , where ring closure was not observed. The chelate complexes were isolated as solids

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[MCl(ligand)]⁺ Complexes (M = Ni, Pd, Pt) with a P,N,N Terdentate Ligand – Solid State and Solution Structures and Catalytic Activity of the Pd^II Derivative in the Heck Reaction

et al. 2005

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NiII, PdII and PtII cationic complexes of the general formula [MCl(PNN)]PF6, where PNN is the terdentate ligand N‐[2‐(diphenylphosphanyl)benzylidene][2‐(2‐pyridyl)ethyl]amine, have been synthesised and fully characterised in solution by NMR spectroscopy. The diamagnetic NiII complex 1 shows fluxionality, which can be attributed to a conformational rearrangement of the two six‐membered chelate rings. On the contrary, the PdII 2 and PtII 3 derivatives are stereochemically rigid on the NMR timescale. The crystal structures of 1 and 2 are reported, which show a planar geometry for both complexes. Complex 2 has been investigated as a precatalyst in the Heck coupling between styrene and bromobenzene. Interestingly, the nature of the solvent has a critical role in determining the yield of the reaction product. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Thermodynamic and spectroscopic studies on the complexation of silver(I) by mixed phosphorus–nitrogen ligands in dimethyl sulfoxide and propylene carbonate

Cited by 9 publications

References 47 publications

Thermodynamics of complex formation of silver(I) with N-donor ligands in non-aqueous solvents

Thermodynamics of complex formation of silver(I) with N-donor ligands in non-aqueous solvents

Ring Closure Kinetics of Bidentate Hemilabile P,N and P,S Ligands on a Platinum(II) Complex

[MCl(ligand)]⁺ Complexes (M = Ni, Pd, Pt) with a P,N,N Terdentate Ligand – Solid State and Solution Structures and Catalytic Activity of the Pd^II Derivative in the Heck Reaction

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Thermodynamic and spectroscopic studies on the complexation of silver(I) by mixed phosphorus–nitrogen ligands in dimethyl sulfoxide and propylene carbonate

Cited by 9 publications

References 47 publications

Thermodynamics of complex formation of silver(I) with N-donor ligands in non-aqueous solvents

Thermodynamics of complex formation of silver(I) with N-donor ligands in non-aqueous solvents

Ring Closure Kinetics of Bidentate Hemilabile P,N and P,S Ligands on a Platinum(II) Complex

[MCl(ligand)]+ Complexes (M = Ni, Pd, Pt) with a P,N,N Terdentate Ligand – Solid State and Solution Structures and Catalytic Activity of the PdII Derivative in the Heck Reaction

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[MCl(ligand)]⁺ Complexes (M = Ni, Pd, Pt) with a P,N,N Terdentate Ligand – Solid State and Solution Structures and Catalytic Activity of the Pd^II Derivative in the Heck Reaction