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Vibrational and structural properties of lead-free piezoelectric (1-x)Na0.5Bi0.5TiO3–xCaTiO3 (0 < x < 1.00) solid solutions have been investigated using Raman spectroscopy and X-ray diffraction. Different anomalies were detected and analyzed taking into consideration the phase transition from rhombohedral to orthorhombic phase at room temperature. All Raman bands were interpreted through the variation in the peak positions (frequency) and the corresponding half-widths at half maximum (HWHM) as a function of x. XRD used as a complementary technique to Raman spectroscopy, showed that the rhombohedral – orthorhombic phase transition went gradually through an intermediate phase consisting of a mixture of rhombohedral (R3c) and orthorhombic (Pnma) structures and that the fraction of orthorhombic phase increased with CT composition. The results show that the morphotropic phase boundary (MPB) is located between 0.09 and 0.15.
The reaction of the alkyl complexes Cp*2LnCH(SiMe 3)2 (Ln = Y 1-Y, Ce 1-Ce, La 1-La; Cp* = η5-C5Me5) and Me2Si(η 5-C5Me4)2LnCH(SiMe3) 2 (Ln = Ce 5-Ce) with 1-methylalk-2-ynes CH3C≡CR (R = Me 3a, Et 3b, nPr 3c, tBu 3d, SiMe3 3e, Ph 3f, C6H4Me-2 3g, C6H3Me 2-2,6 3h, C6H3iPr2-2,6 3i, C6F5 3j) affords the corresponding η3-propargyl/allenyl complexes Cp*2LnCH 2CCR (4a-j-Ln) and Me2Si(η5-C 5Me4)2CeCH2CCR (6a-j-Ce) via propargylic metalation. The hydride complexes [Cp*2Ln(μ-H)] 2 (Ln = Y 2-Y, Ce 2-Ce, La 2-La) react rapidly with 3 to produce mixtures of insertion and propargylic metalation products, and the relative rate of these processes depends on the metal and alkyne substituent. Selected η3-propargy/allenyl complexes Cp*2YCH 2CCR (R = Me 4a-Y, Ph 4f-Y), Cp*2CeCH2CCR (R = Me 4a-Ce, Ph 4f-Ce), Cp*2CeCH(Me)CCEt (9b-Ce), Cp*2LaCH2CCR (R = Ph 4f-La, C6H 3Me2-2,6 4h-La) are obtained on a preparative scale and characterized by NMR spectroscopy, IR spectroscopy, and cryoscopy. Compounds 4f-Y and 4f-La are also characterized by single-crystal X-ray diffraction. The reactions of the η3-propargyl/allenyl complexes with Brønsted acids, such as alcohols and acetylenes, afford the corresponding substituted allenes (RCH=C=CH2) and 1-methylalk-2-ynes (CH 3C≡CR) as organic products. The reactions of 4f-Y and 4f-La with Lewis bases, such as pyridine and THF, yield die corresponding base adducts. The adduct 4f-La · py is characterized by single-crystal X-ray diffraction, revealing an η3-coordinated propargyl/allenyl ligand. © 2008 American Chemical Society.