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Title: The Heptacyanotungstate(IV) Anion: A New 5 d Transition-Metal Member of the Rare Heptacyanometallate Family of Anions

Authors:
 [1];  [2]; ORCiD logo [1]
  1. Department of Chemistry, Texas A&M University, College Station TX 77843 USA
  2. Faculty of Chemistry, Jagiellonian University, Ingardena 3 30-060 Kraków Poland
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400569
Grant/Contract Number:
FG02-02ER45999; SC0012582
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 55; Journal Issue: 38; Related Information: CHORUS Timestamp: 2017-12-01 06:45:57; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Birk, Francisco J., Pinkowicz, Dawid, and Dunbar, Kim R. The Heptacyanotungstate(IV) Anion: A New 5 d Transition-Metal Member of the Rare Heptacyanometallate Family of Anions. Germany: N. p., 2016. Web. doi:10.1002/anie.201602949.
Birk, Francisco J., Pinkowicz, Dawid, & Dunbar, Kim R. The Heptacyanotungstate(IV) Anion: A New 5 d Transition-Metal Member of the Rare Heptacyanometallate Family of Anions. Germany. doi:10.1002/anie.201602949.
Birk, Francisco J., Pinkowicz, Dawid, and Dunbar, Kim R. Thu . "The Heptacyanotungstate(IV) Anion: A New 5 d Transition-Metal Member of the Rare Heptacyanometallate Family of Anions". Germany. doi:10.1002/anie.201602949.
@article{osti_1400569,
title = {The Heptacyanotungstate(IV) Anion: A New 5 d Transition-Metal Member of the Rare Heptacyanometallate Family of Anions},
author = {Birk, Francisco J. and Pinkowicz, Dawid and Dunbar, Kim R.},
abstractNote = {},
doi = {10.1002/anie.201602949},
journal = {Angewandte Chemie (International Edition)},
number = 38,
volume = 55,
place = {Germany},
year = {Thu Jun 30 00:00:00 EDT 2016},
month = {Thu Jun 30 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/anie.201602949

Citation Metrics:
Cited by: 3works
Citation information provided by
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  • The authors report concerning the synthesis and structure of a series of oxosilicate and mixed-oxosilicophosphate compounds of the formula: La{sub 4}Ti{sub 5}Si{sub 4{minus}x}P{sub x}O{sub 22} (x = 0,1). The structure of these complexes was studied by X-ray diffraction. Four-probe electrical conductivity measurements are reported from 13 to 90 K. The structural and conductivity data are correlated.
  • X-ray and microprobe analyses were employed for the investigation of Dy–Mn–Si system at 870/1070/1170 K. The Dy–Mn–Si system, contains the known DyMn{sub 2}Si{sub 2}, DyMnSi and Dy{sub 2}Mn{sub 3}Si{sub 5} compounds and DyMn{sub 4}Si{sub 2}, Dy{sub 2}MnSi{sub 2} and Dy{sub 3}Mn{sub 2}Si{sub 3} were new compounds identified first time and their structure are of the type TmCu{sub 4}Sb{sub 2}, Sc{sub 2}CoSi{sub 2} and Hf{sub 3}Ni{sub 2}Si{sub 3} respectively. The quasi-binary solid solutions were detected at 870/1070/1170 K: the ThMn{sub 12}-type Dy{sub 8}Mn{sub 87}Si{sub 5}, Th{sub 6}Mn{sub 23}-type Dy{sub 23}Mn{sub 72}Si{sub 5}, MgCu{sub 2}-type Dy{sub 33}Mn{sub 58}Si{sub 9} and AlB{sub 2}-typemore » Dy{sub 38}Mn{sub 2}Si{sub 58}. The other binary compounds of the Dy–Mn–Si system do not show any visible solubility. New phases R{sub 2}MnSi{sub 2} and R{sub 3}Mn{sub 2}Si{sub 3} (R=Gd, Tb, Ho–Tm) were found out and their structure of the type Sc{sub 2}CoSi{sub 2} and Hf{sub 3}Ni{sub 2}Si{sub 3} respectively. The specific features of ‘Dy–Transition Metal–Si’ systems were discussed. - Graphical abstract: The isothermal section of Dy–Mn–Si contains the known DyMn{sub 2}Si{sub 2}, DyMnSi, Dy{sub 2}Mn{sub 3}Si{sub 5} and new TmCu{sub 4}Sb{sub 2}-type DyMn{sub 4}Si{sub 2}, Sc{sub 2}CoSi{sub 2}-type Dy{sub 2}MnSi{sub 2} and Hf{sub 3}Ni{sub 2}Si{sub 3}-type Dy{sub 3}Mn{sub 2}Si{sub 3} ternary compounds. The ternary solid solution based on the binary compounds of the Dy–Mn and Dy–Si systems: the ThMn{sub 12}-type Dy{sub 8}Mn{sub 87}Si{sub 5}, Th{sub 6}Mn{sub 23}-type Dy{sub 23}Mn{sub 72}Si{sub 5}, MgCu{sub 2}-type Dy{sub 33}Mn{sub 58}Si{sub 9} and AlB{sub 2}-type Dy{sub 38}Mn{sub 2}Si{sub 58}. The other binary compounds of the Dy–Mn–Si system do not show any visible solubility. New Sc{sub 2}CoSi{sub 2}-type R{sub 2}MnSi{sub 2} and Hf{sub 3}Ni{sub 2}Si{sub 3}-type R{sub 3}Mn{sub 2}Si{sub 3} phases were discovered for R=Gd, Tb, Ho–Tm. Display Omitted - Highlights: • The Dy–Mn–Si section contains three known and three new ternary compounds (phases). • New phase the TmCu{sub 4}Sb{sub 2}-type DyMn{sub 4}Si{sub 2} compound. • New Sc{sub 2}CoSi{sub 2}-type R{sub 2}MnSi{sub 2} and Hf{sub 3}Ni{sub 2}Si{sub 3}-type R{sub 3}Mn{sub 2}Si{sub 3} were detected for R=Gd–Tm. • Dy–Mn–Si supplements the ‘Dy–3d metal–Si’ series and leads to the ‘RT{sub m}X{sub n}’ row's rule.« less
  • Two new layered silicates, La{sub 4}Mn{sub 5}Si{sub 4}O{sub 22} and La{sub 4}V{sub 5}Si{sub 4}O{sub 22}, have been prepared and their structures determined. La{sub 4}Mn{sub 5}Si{sub 4}O{sub 22} and La{sub 4}V{sub 5}Si{sub 4}O{sub 22} crystallize in the monoclinic space group C2/m: a = 14.024(2), b = 5.571(2), c = 11.703(2) {angstrom}, {beta} = 114.34(4){degrees} with Z = 2 formula units per cell and a = 13.510(3), b = 5.605(1), c = 11.114(2) {angstrom}, {beta} = 100.45(3){degrees} with Z = 2 formula units per cell, respectively. The structures were determined by single-crystal X-ray diffraction and refined to residuals of R = 2.73%more » and 3.82%, respectively. The manganese compound crystallizes in the perrierite structure while the vanadium compound crystallizes in the related chevkinite structure. Both perrierite and chevkinite display nearly eclipsed sorosilicate groups which separate rutile-like sheets of edge-shaped transition metal-oxygen octahedra from single, isolated transition metal-oxygen octahedra. Metal-metal distances within the rutile-like sheet are on the order of 2.8 {angstrom} in both compounds, approximately R{sub c}, the critical metal-metal distance defined by Goodenough for appreciable metal-metal interactions and electronic delocalization. Preliminary magnetic data are also presented. 28 refs., 9 figs., 3 tabs.« less
  • Investigations into ternary rare-earth transition-metal antimonide systems RE{sub x}M{sub y}Sb{sub z} have been going on for at least two decades. These studies have been carried out variously to search for new magnetic materials, to test the validity of bonding models, and perhaps most importantly, to systematize an interesting structural chemistry that is not as well understood as that of the corresponding phosphides or arsenides. Some of these antimonides have counterparts in phosphides or arsenides, such as REMSb{sub 2} (M = Mn-Zn, Pd, Ag, Au) with the HfCuSi{sub 2} structure, REM{sub 2}Sb{sub 2} (M = Mn, Ni, Pd) with the CaBe{submore » 2}-Ge{sub 2} and ThCr{sub 2}Si{sub 2} structures, and REM{sub 4}Sb{sub 12} (M = Fe, Ru, Os) with the filled skutterudite LaFe{sub 4}P{sub 12} structure. Others, such as RE{sub 3}M{sub 3}Sb{sub 4} (M = Pt, Cu, Au) and REMSb{sub 3} (M = Cr, V) are unique to antimonides so far. The authors report here the synthesis of a new series of ternary-antimonides RE{sub 3}MSb{sub 5} containing an early transition metal M = Ti, Zr, Hf, Nb. 28 refs., 2 figs., 3 tabs.« less