RETRACTED: A late-transition metal oxo complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9-.
Terminal mono-oxo complexes of the late transition metal elements have long been considered too unstable to synthesize because of repulsion between the oxygen electrons and the mostly filled metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9[O=Pt(H2O)L2], L = [PW9O34(9-)], has now been prepared and isolated at room temperature as air-stable brown crystals. X-ray and neutron diffraction at 30 kelvin revealed a very short [1.720(18) angstrom] Pt-O bond and no evidence of a hydrogen atom at the terminal oxygen, ruling out a better precedented Pt-OH complex. Density functional theory and spectroscopic data account for the stability of the Pt(IV)-oxo unit by electron withdrawal into delocalized orbitals of the polytungstates.
Anderson
Travis M
TM
Department of Chemistry, Emory University, Atlanta, GA 30322, USA.
Neiwert
Wade A
WA
Kirk
Martin L
ML
Piccoli
Paula M B
PM
Schultz
Arthur J
AJ
Koetzle
Thomas F
TF
Musaev
Djamaladdin G
DG
Morokuma
Keiji
K
Cao
Rui
R
Hill
Craig L
CL
D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003460:Crystallization; D018360:Crystallography, X-Ray; D004583:Electrons; D005583:Fourier Analysis; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D015394:Molecular Structure; D033363:Neutron Diffraction; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry; D017671:Platinum Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000302:isolation & purification; D013057:Spectrum Analysis; D013696:Temperature; D014414:Tungsten / Q000737:chemistry; D017973:Tungsten Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000302:isolation & purification
D008024:Ligands; D017671:Platinum Compounds; D017973:Tungsten Compounds; C494785:potassium sodium diaquaoxobis(PW9O34)platinum(IV); D010984:Platinum; D010100:Oxygen; D014414:Tungsten