- Synthesis and physical and structural characterization of Ag(I) complexes supported by non-fluorinated β-diketonate and related ancillary ligands
-
A series of Ag(I) complexes, [Ag(X)L], where X is the anion of 2,2,6,6-tetramethyl-3,5-heptanedione (tmhdH), 2,2,7-trimethyl-3,5- octanedione (tmodH), 2-sila-2,2,6,6-tetramethyl-3,5- heptanedione (tmshdH), 5-mercapto-2,2,6,6-tetramethyl-4-hepten-3-one (S-tmhdH), 5-mercapto-2,2,7-trimethyl-4-octen-3-one (S-tmodH), or 5-amino-2,2,6,6-tetramethyl-4-hepten-3-one (N-tmhdH) and L = triphenylphosphine (PPh3) or tri-n-butylphosphine (PBu3), were prepared by treatment of silver nitrate with either the diketone derivative in the presence of a base or with the preformed sodium salt of the diketone derivative. The thermal properties of the new complexes were investigated for potential application in chemical vapor deposition (CVD) processes. Results of thermogravimetric analysis showed that the vast majority of the silver complexes have little promise for CVD, since the ligands dissociate at elevated temperatures without volatilization. The first ever reported single crystal X-ray diffraction studies of silver complexes, with simple, ancillary, non-fluorinated β-diketonate supporting ligands, revealed [Ag(tmhd)(PPh3)] (1a) to be monomeric and [Ag(S-tmhd)(PPh3)]2 (4a) to be dimeric in the solid state, respectively.
- Ngo, Silvana C.,Banger, Kulbinder K.,Toscano, Paul J.,Welch, John T.
-
p. 1289 - 1297
(2008/10/08)
-
- Nuclear Magnetic Resonance Studies of Terpenes with Chiral and Achiral Lanthanide(III)-Silver(I) Binuclear Shift Reagents
-
Certain binuclear metal β-diketonate complexes consisting of a lanthanide(III) tetrakis chelate anion with a silver(I) counterion are effective NMR shift reagents for olefinic and aromatic substrates.The silver in the pair forms a bond with the olephinic or aromatic,and shifts are observed in the NMR spectrum of the substrate because of the proximity of the paramagnetic lanthanide.Significant alterations are produced in the complex NMR spectra of terpenes such as α- and β-pinene, camphene, and Δ-3-carene in the presence of these shift reagents.In contrast with the excellent shifts in the spectra of olefins and aromatic compounds observed with fluorinated β-diketonate complexes of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione or (trifluoroacetyl)-d-camphor, shifts with 2,2,6,6-tetramethyl-3,5-heptanedione chelates are much smaller.In addition, through proper choice of a choral lanthanide chelate and silver β-diketonate, it is possible to distinguish certain dextro and levo resonances of enantiomers.
- Wenzel, Thomas J.,Sievers, Robert E.
-
p. 382 - 388
(2007/10/02)
-