Journal of the American Chemical Society
Page 4 of 6
Boron‐Phosphorus Compounds and Multiple Bonding. Angew. Chem. Int.
Ed. Engl. 1990, 29, 449-460.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(2) P. Popper, T. A. Ingles, Boron Phosphide, a III–V Compound of Zinc-
Blende Structure. Nature. 1957, 179, 1075.
(
3) a) W. Haubold, W. Keller, G. Sawitzki, The First closo‐
Diphosphahexaborne, P Cl . Angew. Chem. Int. Ed. Engl. 1988, 27, 925-
26; b) B. G. de Boer, A. Zalkin, D. H. Templeton, Crystal and molecular
2
B
4
4
9
4 6 3
structure of phosphorus trifluoride- tris(difluoroboryl)borane, B F -PF .
Inorg. Chem. 1969, 8, 836-841.
3
-
(4) a) H.-G. von Schnering, M. Somer, M. Hartweg, K. Peters, [BP
2
]
and
] , Zintl Anions with Propadiene Structure. Angew. Chem. Int. Ed.
Engl. 1990, 29, 65-67; b) M. Somer, T. Popp, K. Peters, H.-G. von
Schnering, Crystal structure of caesium diphosphidoborate, Cs (BP ). Z.
Kristallogr. 1990, 193, 297-298; c) M. Somer, T. Popp, K. Peters, H.-G.
von Schnering, Crystal structure of sodium diphosphidoborate, Na BP . Z.
3
-
[
BAs
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
2
3
2
Kristallogr. 1990, 193, 281-282; d) M. Somer, M. Hartweg, K. Peters, H.-
G. von Schnering, Crystal structure of potassium diphosphidoborate,
K
3
BP
E.M. Peters, K. Peters, H.G. von Schnering, Crystal structures of
trirubidium diarsenidoborate, Rb BAs and trirubidium diphosphidoborate,
Rb BP . Z. Kristallogr. 1995, 210, 779-780.
2
.Z. Kristallogr. 1990, 191, 311-312; e) M. Somer, W.C. Cabrera,
3
2
3
2
(5) a) A.M. Goforth, H. Hope, C.L. Condron, S.M. Kauzlarich, N. Jensen,
Figure 5. Electronic density of states for the ordered model of
Na BP . Partial contributions of Na, B, and P are shown in blue,
green, and orange colors, respectively. The Fermi level is shown as
a dashed line at 0 eV.
P. Klavins, S. MaQuilon, Z. Fisk. Magnetism and Negative Magnetore-
sistance of Two Magnetically Ordering, Rare-Earth-Containing Zintl
phases with a New Structure Type: EuGa Pn (Pn = P, As). Chem. Mater.
2
2
2
2
2009, 21, 4480-4489; b) H. He, C. Tyson, M. Saito, S. Bobev, Synthesis,
Crystal and Electronic Structures of the New Zintl phases Ba Al Pn (Pn =
P, As) and Ba Ga . Inorg. Chem. 2012, 52, 499-505; c) J. Mathieu, R.
Achey, J.-H. Park, K.M. Purcell, S.W. Tozer, S.E. Latturner, Flux Growth
and Electronic Properties of Ba In Pn (Pn = P, As): Zintl Phases Exhibiting
Metallic Behavior Chem. Mater. 2008, 20, 5675-5681.
3
3
5
3 5
P
ASSOCIATED CONTENT
Supporting Information
3
2
5
5
The Supporting Information is available free of charge on the ACS
Publications website. Crystallographic information files for the ex-
perimentally-determined crystal structure and optimized ordered
(6) S. Lange, M. Bawohl, R. Weihrich, T. Nilges, Mineralization routes to
2 5
polyphosphides: Cu P20 and Cu InP16. Angew. Chem. Int. Ed. Engl. 2008,
47, 5654-5657.
2 2
model of Na BP , experimental details, figures, and tables regard-
(7) a) M. G. Kanatzidis, R. Pöttgen, W. Jeitschko, The metal flux: a prepar-
ative tool for the exploration of intermetallic compounds. Angew. Chem.
Int. Ed. Engl. 2005, 44, 6996-7023; b) T. Mori, Thermoelectric and
magnetic properties of rare earth borides: Boron cluster and layered
compounds. J. Solid State Chem. 2019, 275, 70-82; c) G. Akopov, W.H.
Mak, D. Koumoulis, H. Yin, B. Owens-Baird, M.T. Yeung, M.H. Muni, S.
Lee, I. Roh, Z.C. Sobell, P.L. Diaconescu, R. Mohammadi, K. Kovnir, R.B.
Kaner, Synthesis and Characterization of Single Phase Metal Dodecaboride
ing synthesis, in-house and synchrotron in-situ powder X-ray dif-
fraction, single-crystal X-ray diffraction, crystal structure parame-
ters for the determined structure and superstructural ordered model,
electronic structure and ELF calculations, and diffuse reflectance
UV-vis spectroscopy.
AUTHOR INFORMATION
x x
Solid Solutions: Zr1-xY B12 and Zr1-xU B12. J. Amer. Chem. Soc. 2019, 141,
Corresponding Author
9
047-9062.
Dr. Kirill Kovnir, kovnir@iastate.edu
(8) a) P. R. Jothi, K. Yubuta, B. P. T. Fokwa. A Simple, General Synthetic
Route toward Nanoscale Transition Metal Borides. Adv. Mater. 2018, 30,
Author Contributions
1
704181; b) V. Gvozdetskyi, M. P. Hanrahan, R. A. Ribeiro, T. H. Kim, L.
‡
K.E.W. and J.W. contributed equally to this work.
Zhou, A. J. Rossini, P. C. Canfield, J. V. Zaikina, A Hydride Route to Alkali
Metal Borides: A Case Study of Lithium Nickel Borides. Chem. Eur. J.
2019, 25, 4123; c) V. Gvozdetskyi, G. Bhaskar, M. Batuk, X. Zhao, R.
Wang, S. L. Carnahan, M. P. Hanrahan, R. A. Ribeiro, P. C. Canfield, A. J.
Rossini, C.-Z. Wang, K.-M. Ho, J. Hadermann, J. V. Zaikina. Computation-
ally-driven discovery of the family of layered LiNiB polymorphs. Angew.
Chem. Int. Ed. 2019, DOI: 10.1002/anie.201907499.
ACKNOWLEDGMENT
We would like to thank Dr. W. Xu, Dr. A. Yakovenko, Dr. J.
Dolyniuk, Dr. J. Greenfield, and S. Lee for assistance in
synchrotron data collection, and Prof. J. Vela for access to the
UV/Vis spectrometer. This research was supported by ACS
Petroleum Research Fund, grant 55036-DNI10, and Iowa State
University. Use of the Advanced Photon Source at Argonne
National Laboratory was supported by the US Department of
Energy, Office of Science, Office of Basic Energy Sciences, under
Contract No. DE-AC02-06CH11357.
(9) a) L. Lindsay, D. A. Broido, T. L. Reinecke, First-Principles Determi-
nation of Ultrahigh Thermal Conductivity of Boron Arsenide: A Competi-
tor for Diamond? Phys. Rev. Lett. 2013, 111, 025901; b) J. S. Kang, H. Wu,
Y. Hu, Thermal Properties and Phonon Spectral Characterization of Syn-
thetic Boron Phosphide for High Thermal Conductivity Applications. Nano
Lett. 2017, 17, 7507-7514.
(10) a) J. S. Kasper, P. Hagenmuler, M. Pouchard, C. Cros, Clathrate Struc-
ture of Silicon Na
Si46 and Na Si136 (x < 11). Science, 1965, 150, 1713-1714;
8 x
b) M. Beekman, M. Baitinger, H. Borrmann, W. Schnelle, K. Meier, G. S.
Nolas, Y. Grin, Preparation and Crystal Growth of Na24Si136. J. Amer.
Chem. Soc. 2009, 131, 9642-9643.
REFERENCES
(
1) a) C. R. Groom, I. J. Bruno, M. P. Lightfoot, S. C. Ward, The Cambridge
Structural Database. Acta Cryst. 2016, B72, 171-179; b) M. Driess, H. Pritz-
kow, W. Siebert, Novel Boron‐Phosphorus Cages with C and C
4
B
4
P
4
2
B
4
P
4
(11) a) A. M. Guloy, R. Ramlau, Z. Tang, W. Schnelle, M. Baitinger, Y.
Grin, A guest-free germanium clathrate. Nature 2006, 443, 320-323; b) A.
Ammar, C. Cros, M. Pouchard, N. Jaussaud, J. M. Bassat, G. Villeneuve,
M. Duttine, M. Menetrier, E. Reny, On the clathrate form of elemental sili-
con, Si136: preparation and characterisation of Na Si (x→0). Solid State
Frameworks Angew. Chem. Int. Ed. Engl. 1988, 27, 399-400; c) H. Schmid-
baur, T. Wimmer, A. Grohmann, O. Steigelmann, G. Müller, Phosphane‐
borane chemistry. Open‐chain and cyclic phosphane‐boranes based on tet-
ramethyldiphosphane. Chem. Ber. 1989, 122, 1607-1612; d) P. P. Power,
x
136
Sci. 2004, 6, 393-400.
ACS Paragon Plus Environment