PbF[Br2F7], a Fluoridobromate(III) of a p-Block Metal
PbF[Br2F7], a Fluoridobromate(III) of a p-Block Metal
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DOI：
10.1002/ejic.201901041
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发表时间：
2019-12-05
影响因子：
2.3
通讯作者：
Kraus, Florian
中科院分区：
文献类型：
--
作者：
Bandemehr, Jascha;Sachs, Malte;Kraus, Florian
化合物PbF[Br 2F 7]代表p区元素的第一氟代溴酸盐（III）。它是由PbF 2和BrF 3直接反应合成的，在无色粉末中呈针状晶体。粉末X-射线衍射、红外光谱和拉曼光谱表明，该化合物几乎是纯的，副产物为Pb_3F_8和Pb_2F_6。用X射线衍射法测定了其单晶结构。PbF[Br_2F_7]晶体属P_2（1）/c（No.14）空间群，在100 K时，a = 4.3698（3），B = 13.3767（7），c = 12.0836（8）埃，β = 97.509（5）度，V = 700.27（8）埃（3），Z = 4。PbF[Br 2F 7]在50 ℃以上分解，由于BrF 3的损失，纯PbF 2仍然存在。对该化合物的晶体结构进行量子化学计算，以分配振动光谱的频带，并获得电子密度差图，该电子密度差图可视化Pb原子周围的电子密度。CHARDI计算支持分配的氧化态+II，+III，和-I的铅，溴，和F原子，分别。
The compound PbF[Br2F7] represents the first fluoridobromate(III) of a p-block element. It was synthesized in form of needle-shaped crystals among its colorless powder from the direct reaction of PbF2 with BrF3. Powder X-ray diffraction, IR and Raman spectroscopy show that it was obtained in almost pure form with Pb3F8 and Pb2F6 as by-products. The single crystal structure was determined by X-ray diffraction. PbF[Br2F7] crystallizes in space group P2(1)/c (No. 14) with a = 4.3698(3), b = 13.3767(7), c = 12.0836(8) angstrom, beta = 97.509(5)degrees, V = 700.27(8) angstrom(3), Z = 4 at T = 100 K. PbF[Br2F7] decomposes above 50 degrees C due to loss of BrF3 and pure PbF2 remains. Quantum chemical calculations were performed on the crystal structure of the compound to assign the bands of the vibrational spectra and to obtain electron density difference maps that visualize the electron density around the Pb atoms. CHARDI calculations support the assignment of the oxidation states +II, +III, and -I to the Pb, Br, and F atoms, respectively.