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Title: Symmetry and magnetism in Ni 9 Te 6 clusters ligated by CO or phosphine ligands

 [1];  [1];  [1]
  1. Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284-2000, USA
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Sponsoring Org.:
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Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 2; Related Information: CHORUS Timestamp: 2018-02-14 09:25:13; Journal ID: ISSN 0021-9606
American Institute of Physics
Country of Publication:
United States

Citation Formats

Reber, Arthur C., Chauhan, Vikas, and Khanna, Shiv N.. Symmetry and magnetism in Ni 9 Te 6 clusters ligated by CO or phosphine ligands. United States: N. p., 2017. Web. doi:10.1063/1.4973609.
Reber, Arthur C., Chauhan, Vikas, & Khanna, Shiv N.. Symmetry and magnetism in Ni 9 Te 6 clusters ligated by CO or phosphine ligands. United States. doi:10.1063/1.4973609.
Reber, Arthur C., Chauhan, Vikas, and Khanna, Shiv N.. Sat . "Symmetry and magnetism in Ni 9 Te 6 clusters ligated by CO or phosphine ligands". United States. doi:10.1063/1.4973609.
title = {Symmetry and magnetism in Ni 9 Te 6 clusters ligated by CO or phosphine ligands},
author = {Reber, Arthur C. and Chauhan, Vikas and Khanna, Shiv N.},
abstractNote = {},
doi = {10.1063/1.4973609},
journal = {Journal of Chemical Physics},
number = 2,
volume = 146,
place = {United States},
year = {Sat Jan 14 00:00:00 EST 2017},
month = {Sat Jan 14 00:00:00 EST 2017}

Journal Article:
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Publisher's Version of Record at 10.1063/1.4973609

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  • [Pd{sub 16}Ni{sub 4}(CO){sub 22}(PPh{sub 3}){sub 4}]{sup 2-} (1) and [Pd{sub 33}Ni{sub 9}(CO){sub 41}(PPh{sub 3}){sub 6}]{sup 4-} (2) were obtained as the two major products from the reduction of PdCl{sub 2}(PPh{sub 3}){sub 2} with [Ni{sub 6}(CO){sub 12}]{sup 2-}. Their crystal structures as [PPh{sub 4}]{sup +} salts were unambiguously determined from CCD X-ray crystallographic analyses; the resulting stoichiometries were ascertained from elemental analyses. Infrared, multinuclear {sup 1}H, {sup 31}P{l_brace}{sup 1}H{r_brace} NMR, UVvis, CV, variable-temperature magnetic susceptibility, and ESI FT/ICR mass spectrometric measurements were performed. The Pd{sub 16}Ni{sub 4} core of 1 ideally conforms to a ccp {nu}{sub 3} tetrahedron of pseudo-T{sub d}more » ({sub {ovr 4}}3m) symmetry. Its geometry normal to each tetrahedral Pd7Ni3 face (i.e., along each of the four 3-fold axes) may be viewed as a four-layer stacking of 20 metal atoms in a ccp [a(Ni{sub 1}) b(Pd{sub 3}) c(Pd{sub 6}) a(Pd{sub 7}Ni{sub 3})] sequence. A comparative analysis of the different ligand connectivities about the analogous metal-core geometries in 1 and the previously reported [Os{sub 20}(CO){sub 40}]{sup 2-} has stereochemical implications pertaining to the different possible modes of carbon monoxide attachment to ccp metal(111) surfaces. The unique geometry of the Pd{sub 33}Ni{sub 9} core of 2, which has pseudo-D{sub 3h} ({sub {ovr 6}}2m) symmetry, consists of five equilateral triangular layers that are stacked in a hcp [a(Pd{sub 7}Ni{sub 3}) b(Pd{sub 6}) a(Pd{sub 7}Ni{sub 3}) b(Pd{sub 6}) a(Pd{sub 7}Ni{sub 3})] sequence. Variable-temperature magnetic susceptibility measurements indicated both 1 and 2 to be diamagnetic over the entire temperature range from 5.0 to 300 K. Neutral Pd{sub 12}(CO){sub 12}(PPh{sub 3}){sub 6} (3) and [Pd{sub 29}(CO){sub 28}(PPh{sub 3}){sub 7}]{sup 2-} (4) as the [PPh{sub 4}]{sup +} salt were obtained as minor decomposition products from protonation reactions of 1 and 2, respectively, with acetic acid. Compound 3 of pseudo-D{sub 3d} ({sub {ovr 3}}2/m) symmetry represents the second highly deformed hexacapped octahedral member of the previously established homopalladium family of clusters containing uncapped, monocapped, bicapped, and tetracapped Pd6 octahedra. The unprecedented centered 28-atom polyhedron for the Pd{sub 29} core of 4 of pseudo-C{sub 3v} (3m) symmetry may be described as a four-layer stacking of 29 metal atoms in a mixed hcp/ccp [a(Pd{sub 1}) b(Pd{sub 3}) a(Pd{sub 10}) c(Pd{sub 15})] sequence.« less
  • Several new water-soluble iridium(I) complexes were synthesized and their reactivities with small molecules (H{sub 2} or CO) in polar solvents (DMSO or H{sub 2}O) examined. Reaction of H{sub 2} with [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3} (TPPMS = P(C{sub 6}H{sub 5}){sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K)) in DMSO or H{sub 2}O produces [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, while the reaction of CO with [Ir(CO)(TPPMS){sub 3}]-CF{sub 3}SO{sub 3} in water yields [Ir(CO){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}. Carbonylation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} in DMSO produces [Ir(CO){sub 3}(TPPMS){sub 2}]ClO{sub 4} and TPPMS; no reaction is observed in H{sub 2}O. Hydrogenation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4}more » in DMSO or H{sub 2}O yields [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]ClO{sub 4}, while reaction of H{sub 2} with an aqueous solution of [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3} produces [Ir(CO)(H{sub 2}O)(H){sub 2}(TPPTS){sub 2}]CF{sub 3}SO{sub 3}. Reaction of trans-Ir(CO)ClL{sub 2} (L = TPPMS or TPPTS) with excess L in H{sub 2}O produces [Ir(CO)L{sub 3}]Cl, while no reaction occurs in DMSO, [Ir(CO){sub 3}(TPPMS){sub 2}]Cl reacts irreversibly with TPPMS in H{sub 2}O to produce [Ir(CO){sub 2}-(TPPMS){sub 3}]Cl.« less
  • The Te-centered, cubic cluster Ni{sub 8}Te({mu}{sub 4}-Te){sub 6}(L){sub 8} is suggested as a stable molecule, on the basis of extended Hueckel molecular orbital calculations for the cluster and its experimentally known, Ni-centered analogue, Ni{sub 9}({mu}{sub 4}-Te){sub 6}(PEt{sub 3}){sub 8}. Calculations show that the interstitial Ni or Te atom binds to the empty cluster at the expense of Ni-Ni and Ni-Te bonding within the cluster framework. The interstitial Ni atom compensates by bonding weakly to the framework nickels, primarily through its a{sub 1g} (4s) orbital; the central Te bonds strongly to both the nickel cube and the face-capping telluriums. Large HOMO-LUMOmore » gaps suggest that 130 of 114 electrons are optimum for Ni{sub 8}Te({mu}{sub 4}-Te){sub 6}(L){sub 8}. Analogies to the solid-state structures of NiTe and CsCl, as well as to the centered octahedral clusters Zr{sub 6}I{sub 12}Z (Z = main-group or transition-metal atom), are pointed out.« less
  • The reactions of the compounds M{sub 3}(CO){sub 10}({mu}{sub 3}-S) (1a, M = Fe; 1b, M = Ru) with MeC{sub 2}NMe{sub 2} yielded the products M{sub 2}(CO){sub 6}({mu}-SC(NMe{sub 2})CMe) (2a, M = Fe, 3%; 2b, M = Ru, 36%) and M{sub 3}(CO){sub 9}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (3a, M = Fe, 30%; 3b, M = Ru, 14%). The reaction of Os{sub 3}(CO){sub 10}({mu}{sub 3}-S) (1c) with MeC{sub 2}NMe{sub 2} yielded only the trinuclear product Os{sub 3}(CO){sub 9}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (3c, 87%). Compounds 2b and 3c were characterized by single-crystal X-ray diffraction analyses. Crystal data: for 2b, space group P{barmore » 1}, a = 9.189 (1) {angstrom}, b = 11.705 (3) {angstrom}, c = 8.213 (1) {angstrom}, {alpha} = 106.18 (1){degree}, {beta} = 110.06 (1){degree}, {gamma} = 79.60 (2){degree}, V = 793.3 (3) {angstrom}{sup 3}, Z = 2. For 3c, space group P{bar 1}, a = 9.397 (4) {angstrom}, b = 13.406 (7) {angstrom}, c = 8.914 (3) {angstrom}, {alpha} = 92.84 (4){degree}, {beta} = 115.20 (3){degree}, {gamma} = 97.54 (4){degree}, V = 1000.3 (8) {angstrom}{sup 3}, Z = 2.« less
  • The techniques used for the preparation of metal-rich chalcides by high-temperature techniques are discussed. The two newest metal-rich compounds, two ternary metal-rich sulfides with novel structures, are described.