38 research outputs found

    An Addendum to Harrington\u27s Northern Salinan Place Names

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    Rivers and Jones (1993) reported the locations of 21 place names in the upper San Antonio Valley and adjacent coast of Monterey County, California, that were noted by Salinan speakers in John Peabody Harrington\u27s field notes from 1922 to 1932. Surface reconnaissance and review of recently completed archaeological survey reports have led to the identification of 11 additional Salinan places in the upper San Antonio Valley and refinement in the location of three others. Archaeological sites in the vicinity of named places tentatively suggest that Salinan settlements are marked by clusters of small middens and bedrock mortars

    Metal-metal Bonding in Tetracyanometallates (M=PtII, PdII, NiII) of monovalent Thallium. Chrystallographic and Spectroscopic Characterization of the new Compounds Tl2Ni(CN)4 and Tl2Pd(CN)4

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    The new crystalline compounds Tl2Ni(CN)(4) and Tl2Pd(CN)(4) were synthesized by several procedures. The structures of the compounds were determined by single-crystal X-ray diffraction. The compounds are isostructural with the previously reported platinum analogue, Tl2Pt(CN)(4). A new synthetic route to the latter compound is also suggested. In contrast to the usual infinite columnar stacking of [M(CN)(4)](2-) ions with short intrachain M-M separations, characteristic of salts of tetracyanometalates of Ni-II, Pd-II, and Pt-II, the structure of the thallium compounds is noncolumnar with the two Tl-I ions occupying axial vertices of a distorted pseudo-octahedron of the transition metal, [MTl2C4]. The Tl-M distances in the compounds are 3.0560(6), 3.1733(7), and 3.140(1) A for Ni-II, Pd-II, and Pt-II, respectively. The short Tl-Ni distance in Tl2Ni(CN)(4) is the first example of metal-metal bonding between these two metals. The strength of the metal-metal bonds in this series of compounds was assessed by means of vibrational spectroscopy. Rigorous calculations, performed on the molecules in D-4h point group symmetry, provide force constants for the Tl-M stretching vibration constants of 146.2, 139.6, and 156.2 N/m for the Ni-II, Pd-II, and Pt-II compounds, respectively, showing the strongest metal-metal bonding in the case of the Tl-Pt compound. Amsterdam density-functional calculations for isolated Tl2M(CN)(4) molecules give Tl-M geometry-optimized distances of 2.67, 2.80, and 2.84 A for M = Ni-II, Pd-II, and Pt-II, respectively. These distances are all substantially shorter than the experimental values, most likely because of intermolecular Tl-N interactions in the solid compounds. Time-dependent density-functional theory calculations reveal a low-energy, allowed transition in all three compounds that involves excitation from an a(1g) orbital of mixed Tl 6p(z)-M nd(z)(2) character to an a(2u) orbital of dominant Tl 6p(z) character
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