TY - JOUR
T1 - The nature of species derived from [Pt(bipy)2]2+ in aqueous solution
T2 - X-ray structural, mass spectral, NMR, and computational studies
AU - Cavigliasso, Germán
AU - Stranger, Robert
AU - Lo, Warrick K.C.
AU - Crowley, James D.
AU - Blackman, Allan G.
PY - 2013
Y1 - 2013
N2 - The reaction of [Pt(bipy)2]2+ with a variety of organic and inorganic ligands in aqueous solution has been studied by 195Pt, 1H and 13C NMR, X-ray crystallography, UV-Vis spectroscopy and high-resolution mass spectrometry. 195Pt NMR spectra of D2O solutions containing equimolar amounts of [Pt(bipy)2]2+ and the heterocyclic N donor ligands pyridine, 3-methylpyridine and 4-methylpyridine give evidence for the formation of at least one species, while quinoline appears to give only a single product under the same conditions. These results are supported by 1H and 13C NMR data. The complex [Pt(bipy)(py)2](ClO 4)2 was isolated from a reaction mixture containing equimolar amounts of [Pt(bipy)2]2+ and pyridine, and was characterised by X-ray crystallography. The 195Pt NMR chemical shift of this material suggested the presence of [Pt(bipy)(R-py)2] 2+ species in aqueous solutions containing equimolar amounts of [Pt(bipy)2]2+ and R-py (R-py = py, 3-Mepy, 4-Mepy). High-resolution mass spectral analysis of aqueous solutions containing [Pt(bipy)2]2+ and inorganic ligands L (L = OH-, S2O32-, N3-, SCN-, CN-, Cl- and SO42-) gives strong evidence for the formation of pseudo five-coordinate complexes of the type [Pt(bipy-κ2N,N′)(bipy-κN)(L)] n+ in the cases of OH-, S2O32-, N3- and SCN-. The results of calculations aimed at determining the 195Pt NMR chemical shifts of the possible species resulting from the reaction of [Pt(bipy)2]2+ with OH- in aqueous solution are consistent with the formation of pseudo five-coordinate [Pt(bipy-κ2N,N′)(bipy-κN)(OH)]+, but are not absolutely conclusive. However, the bonding energy of this complex is calculated to be significantly lower than that of any species resulting from OH- attack at a bipy ligand of [Pt(bipy)2]2+.
AB - The reaction of [Pt(bipy)2]2+ with a variety of organic and inorganic ligands in aqueous solution has been studied by 195Pt, 1H and 13C NMR, X-ray crystallography, UV-Vis spectroscopy and high-resolution mass spectrometry. 195Pt NMR spectra of D2O solutions containing equimolar amounts of [Pt(bipy)2]2+ and the heterocyclic N donor ligands pyridine, 3-methylpyridine and 4-methylpyridine give evidence for the formation of at least one species, while quinoline appears to give only a single product under the same conditions. These results are supported by 1H and 13C NMR data. The complex [Pt(bipy)(py)2](ClO 4)2 was isolated from a reaction mixture containing equimolar amounts of [Pt(bipy)2]2+ and pyridine, and was characterised by X-ray crystallography. The 195Pt NMR chemical shift of this material suggested the presence of [Pt(bipy)(R-py)2] 2+ species in aqueous solutions containing equimolar amounts of [Pt(bipy)2]2+ and R-py (R-py = py, 3-Mepy, 4-Mepy). High-resolution mass spectral analysis of aqueous solutions containing [Pt(bipy)2]2+ and inorganic ligands L (L = OH-, S2O32-, N3-, SCN-, CN-, Cl- and SO42-) gives strong evidence for the formation of pseudo five-coordinate complexes of the type [Pt(bipy-κ2N,N′)(bipy-κN)(L)] n+ in the cases of OH-, S2O32-, N3- and SCN-. The results of calculations aimed at determining the 195Pt NMR chemical shifts of the possible species resulting from the reaction of [Pt(bipy)2]2+ with OH- in aqueous solution are consistent with the formation of pseudo five-coordinate [Pt(bipy-κ2N,N′)(bipy-κN)(OH)]+, but are not absolutely conclusive. However, the bonding energy of this complex is calculated to be significantly lower than that of any species resulting from OH- attack at a bipy ligand of [Pt(bipy)2]2+.
KW - Calculations
KW - Five-coordinate
KW - Mass spectrometry
KW - Platinum
KW - X-ray structure
UR - http://www.scopus.com/inward/record.url?scp=84885022648&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2013.05.004
DO - 10.1016/j.poly.2013.05.004
M3 - Article
SN - 0277-5387
VL - 64
SP - 238
EP - 246
JO - Polyhedron
JF - Polyhedron
ER -