TY  - JOUR
AU  - Görne, Arno L.
AU  - George, Janine
AU  - van Leusen, Jan
AU  - Dück, Gerald
AU  - Jacobs, Philipp
AU  - Kumar, Naveen
AU  - Dronskowski, Richard
TI  - Ammonothermal Synthesis, Crystal Structure, and Properties of the Ytterbium(II) and Ytterbium(III) Amides and the First Two Rare-Earth-Metal Guanidinates, YbC(NH)$_{3}$ and Yb(CN$_{3}$ H$_{4}$)$_{3}$
JO  - Inorganic chemistry
VL  - 55
IS  - 12
SN  - 1520-510X
CY  - Washington, DC
PB  - American Chemical Society
M1  - FZJ-2016-07439
SP  - 6161 - 6168
PY  - 2016
AB  - We report the oxidation-controlled synthesis of the ytterbium amides Yb(NH2)2 and Yb(NH2)3 and the first rare-earth-metal guanidinates YbC(NH)3 and Yb(CN3H4)3 from liquid ammonia. For Yb(NH2)2, we present experimental atomic displacement parameters from powder X-ray diffraction (PXRD) and density functional theory (DFT)-derived hydrogen positions for the first time. For Yb(NH2)3, the indexing proposal based on PXRD arrives at R3̅, a = 6.2477(2) Å, c = 17.132(1) Å, V = 579.15(4) Å3, and Z = 6. The oxidation-controlled synthesis was also applied to make the first rare-earth guanidinates, namely, the doubly deprotonated YbC(NH)3 and the singly deprotonated Yb(CN3H4)3. YbC(NH)3 is isostructural with SrC(NH)3, as derived from PXRD (P63/m, a = 5.2596(2) Å, c = 6.6704(2) Å, V = 159.81(1) Å3, and Z = 2). Yb(CN3H4)3 crystallizes in a structure derived from the [ReO3] type, as studied by powder neutron diffraction (Pn3̅, a = 13.5307(3) Å, V = 2477.22(8) Å3, and Z = 8 at 10 K). Electrostatic and hydrogen-bonding interactions cooperate to stabilize the structure with wide and empty channels. The IR spectra of the guanidinates are compared with DFT-calculated phonon spectra to identify the vibrational modes. SQUID magnetometry shows that Yb(CN3H4)3 is a paramagnet with isolated Yb3+ (4f13) ions. A CONDON 2.0 fit was used to extract all relevant parameters.
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000378369900054
C6  - pmid:27248288
DO  - DOI:10.1021/acs.inorgchem.6b00736
UR  - https://juser.fz-juelich.de/record/824943
ER  -