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  • Author: Nils Heinrich x
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Abstract

(MgBrdiglyme)2 (1) crystallized in low yield from an ether solution of the Grignard compound mesMgBr (mes = mesityl) on adding diglyme. It is more conveniently prepared from an ether solution of MgBr2 by addition of diglyme. The mixed solvate MgBrdiglyme thf (2) crystallized from a diglyme/tetrahydrofuran solution of 1 after addition of ether. An X-ray structure determination of 1 reveals dimeric units containing hexacoordinated Mg atoms surrounded by three oxygen atoms and three bromide atoms, with each kind of atoms arranged in a meridional fashion. The two octahedral MgO3Br3 units share a common edge with two Br atoms. Compound 2 is a mononuclear complex with the Br atoms in cis-position. The diglyme ligand occupies meridional positions of a distorted MgBr2O4 octahedron.

Zusammenfassung:

In Deutschland sind aktuell mehr als 1,5 Millionen Menschen an Demenz erkrankt. Es ist durch die demografischen Prozesse in den nächsten Jahrzehnten jährlich von über 300.000 Neuerkrankungen auszugehen. Gelingen keine revolutionären Fortschritte in Prävention und Therapie, sind extreme Auswirkungen auf die Gesundheitsversorgung zu erwarten. Die Gesundheitspolitik ist gefordert, adäquate Anreize für eine nachhaltige Finanzierung der Pflege und für ausreichendes Pflegepersonal zu schaffen.

Abstract

Long waiting times are a common feature and a major concern in many public health care systems. They are often characterized as inefficient because they are a burden to patients without generating any gains for providers. There is an ongoing debate in Germany regarding the preferential treatment given to private health insurance (PHI) holders while statutory health insurance (SHI) holders face continuously increasing waiting times. In order to tackle this problem in the outpatient sector, Germany initiated a reform in 2015 which was aimed at providing SHI holders with appointments within an acceptable time frame. We exploit longitudinal experimental data to examine waiting times for six elective outpatient treatments in Germany for PHI and SHI holders before and after the reform. We find a considerable difference in waiting times favoring private patients. For SHI holders, waiting times remained stable over time (27.5 days in 2014, 30.7 days in 2016, Δ 3.2 days, p-value=0.889) while PHI holders experienced a significant improvement (13.5 days in 2014; 7.8 days in 2016; Δ 5.7 days, p-value=0.002). The results indicate that even after the reform there is still an unequal access to elective outpatient treatment depending on the patient’s insurance status.

Abstract

The metalation of tri-terr-butylsilylphosphane with bis[bis(trimethylsilyl)amino]stannylen yields nearly quantitatively the tetrameric tin(II) tri-terf-butylsilylphosphandiide with a central Sn4P4 cubane moiety. Barium bis[tri-tert-butylsilylphosphanide] is accessible via the reaction of tri-tert-butylsilylphosphane with barium bis[bis(trimethylsilyl)amide] in the molar ratio 2 : 1 . This phosphanide reacts with bis[bis(trimethylsilyl)amino]stannylen to give barium tritin(II) tetrakis[μ3-tri-tert-butylsilylphosphandiide]. Crystallographic data of 1: P 212121, T = 193 K, a = 1532.6(3), b = 2120.2(4), c = 2194.0(5) pm, V = 7.129(3) nm3, Z = 4, R, = 0.0360 (9132 observed data [I > 2a( f) ] ) , wR2 = 0.1064 (all data); crystallographic data of 3: P 21/c, T = 193 K, a = 1927.35(1), b = 1799.27(2), c = 2201.35(2) pm, β = 93.010(1)°, V = 7.6234(1) nm3, Z = 4, R1 = 0.0321 (11993 observed data [I > 2σ(/)]), wR2 = 0.0772 (all data).

Abstract

Water and oxygen sensitive compounds (tBu3SiEX2)2, tBu3SiEX2 Do and (tBu3Si)2EX (E = AI, Ga, In; X = (F), Cl, Br; Do = OR2, NR3) have been synthezised by reaction of EX3 with tBu3SiNa in the absence or presence of donors. In addition, (tBu3Si)AlBr2, (tBu3Si)2InF and tBu3SiInBr2 were prepared by reaction of AlBr3 with (tBu3Sij2Zn or of (tBu3Si)2In- In(Si/Bu3)2 with AgF2 and HBr, respectively. The adduct [tBu3SiAlBr2 · AlBr3 ·1/2MgBr2]2 is formed from AlBr3 and (tBu3Si)2Mg(THF)2. Thermal decomposition of the compounds in solution or in the gas phase leads to the formation of tBu3SiEX2 (from the dimers or the donor adducts) and of tBu3SiX. The Lewis acidity of tBu3SiEX2 against donors increases in the direction Do = Et2O < THF < NEtMe2. Dehalogenation of (tBu3Si)2ECl with tBu3SiNa(THF)2 in pentane at room temperature leads to clusters (tBu3Si)4Al2, (tBu3Si)3Ga2 , (tBu3Si)4In2 and (tBu3Si)3Ga2Na(THF)3, reduction of tBu3SiGaCl2 with Na or K in heptane at 100°C to the tetrahedran (tBu3Si)4Ga4. The structures of (tBu3SiGaCl2)2, (tBu3Si)2GaCl, and [tBu3SiAlBr2 AlBr3 ·1/2MgBr2]2 have been determined by X-ray structure analysis.

The orange THF adduct (tBu3Si)3P5Na2 (THF)4 of the pentaphosphide (tBu3Si)3P5Na2 (3) has been prepared, (i) by protolysis of the tetraphosphide (tBu3Si)2P4Na2(THF)n (2) with CF3CO2H in THF (molar ratio 2 : 1 ) , (ii) by dissolving crystalline 2 in toluene, and (iii) by the reaction of P4 with tBu3SiNa(THF)2 in benzene (molar ratio 1 : 4). According to an X-ray structural analysis, the THF adduct of 3 contains a P3 ring with two PNa(SitBu3) substituents in cis position and one SitBu3 substituent in trans position to the former groups. The protolysis of 3 with CF3CO2H leads to the pentaphosphane P5H2(SitBu3)3 (9), the silylation of 3 with Me2SiCl2 to the pentaphosphane P5 (SiMe2)(SitBu3)3 (10), and the oxidation of 3 with C2(CN)4 to the pentaphosphane P5(SitBu3)3 (5). The structures of 3,5,9, and 10 have been assigned from 31P and 29Si NMR data. The pentaphosphane 5 contains a hitherto unknown P5 backbone of a P3 ring anellated with a P4 ring.

Water- and oxygen-sensitive compounds of the type R ’nEHal3-n (R' = SitBu2Ph; E = Triel) with or without donors, viz. RAlBr2, R'3Al, R'GaCl2'THF, R'GaCl2, R'3Ga, R'InCl2·THF and R'3In have been synthesized by reaction of EX3 with NaSitBu2Ph (prepared for this purpose) in the absence or presence of donors. The dihalides R'EHal2 have also been obtained by reaction of R'3E with EHal3, whereas monohalides R'2EHal are not accessible via these and other routes up to date. All trielanes have been characterized by NMR and the structures of the R'3E compounds have been determined by X-ray analyses.