29Si, 47Ti, 49Ti and 195Pt solid state MAS NMR spectroscopic investigations of ternary silicides TPtSi, germanides TPtGe (T = Ti, Zr, Hf) and stannide TiPtSn. Issue 19 (21st April 2016)

• Record Type: Journal Article
• Authors: Benndorf, Christopher; Eckert, Hellmut; Pöttgen, Rainer
• Is Part Of: Dalton transactions. Volume 45:Issue 19(2016)
• Page Start: 8215
• Page End: 8223
• Publication Date: 2016-04-21
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt00861e
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Silicides TPtSi, germanides TPtGe (T = Ti, Zr, Hf) and stannide TiPtSn show well resolved 29 Si, 47 Ti, 49 Ti and 195 Pt solid state MAS NMR spectra. Abstract : Eight ternary tetrelides TPtX (T = Ti, Zr, Hf; X = Si, Ge, Sn) were synthesized from the elements by arc-melting and subsequent annealing. TiPtSi, ZrPtSi, ZrPtGe, HfPtSi and HfPtGe crystallize with the orthorhombic TiNiSi type structure, in the space group Pnma . The structures of HfPtSi ( a = 654.44(9), b = 387.97(6), c = 750.0(1) pm, w R 2 = 0.0592, 411 F 2 values, 20 variables) and HfPtGe ( a = 660.36(7), b = 395.18(4), c = 763.05(8) pm, w R 2 = 0.0495, 430 F 2 values, 20 variables) were refined from single crystal X-ray diffractometer data. TiPtSn adopts the cubic MgAgAs type. TiPtGe is dimorphic with a TiNiSi type high-temperature modification which transforms to cubic LT-TiPtGe (MgAgAs type). All phases were investigated by high resolution 29 Si, 47 Ti, 49 Ti and 195 Pt solid state MAS NMR spectroscopy. In the cubic compounds, the 47/49 Ti NMR signals are easily detected owing to the absence of quadrupolar broadening effects. The 195 Pt resonances of the orthorhombic compounds are characterized by strongly negative isotropic Knight shifts and large Knight shift anisotropies, whereas positive isotropic Knight shifts and no anisotropies are observed for the cubic compounds. These results indicate that the phase transition in TiPtGe is associated with dramatic changes in the electronic properties. Within each group of isotypic compounds the isotropic 29 Si, 47/49 Ti and 195 Pt Knight shifts show systematic dependences on the transition metal or tetrel atomic number, suggesting that the numerical values are influenced by the electronegativities of the metallic (or metalloid) neighbours.