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Dr. Felix Anke Dr. Susanne Boye Dr. Anke Spannenberg Dr. Albena Lederer Prof. Dr. Detlef Heller PD Dr. Torsten Beweries 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(35):7889-7899
Dehydropolymerisation of methylamine borane (H3B⋅NMeH2) using the well-known iron amido complex [(PNP)Fe(H)(CO)] (PNP=N(CH2CH2PiPr2)2) ( 1 ) gives poly(aminoborane)s by a chain-growth mechanism. In toluene, rapid dehydrogenation of H3B⋅NMeH2 following first-order behaviour as a limiting case of a more general underlying Michaelis–Menten kinetics is observed, forming aminoborane H2B=NMeH, which selectively couples to give high-molecular-weight poly(aminoborane)s (H2BNMeH)n and only traces of borazine (HBNMe)3 by depolymerisation after full conversion. Based on a series of comparative experiments using structurally related Fe catalysts and dimethylamine borane (H3B⋅NMe2H) polymer formation is proposed to occur by nucleophilic chain growth as reported earlier computationally and experimentally. A silyl functionalised primary borane H3B⋅N(CH2SiMe3)H2 was studied in homo- and co-dehydropolymerisation reactions to give the first examples for Si containing poly(aminoborane)s. 相似文献
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Carsten von Hänisch PD Dr. 《无机化学与普通化学杂志》2008,634(1):23-29
The range of molecular silicon phosphorus compounds has been extended by some new species containing oligosilane ((R2Si)n; n ≥ 2) or oligosiloxane ((R2SiO)mSiR2; m ≥ 1) fragments bound to phosphorus atoms. Primary and secondary compounds of these types allow for the synthesis of metal derivatives. Such metalated species usually form oligomers and exhibit a versatile structural chemistry with cyclic, polycyclic, and cage‐like patterns. The main results obtained in the field of oligosilane‐ and oligosiloxane‐bridged phosphines will be presented below and the structures of the metal derivatives will be discussed. Moreover, the synthesis of an inorganic ligand on the basis of siloxane‐bridged phosphines will be presented. This compound opens up a new chapter in host‐guest chemistry. 相似文献
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C. Peter Sebastian Gunter Heymann Birgit Heying Ute Ch. Rodewald Hubert Huppertz PD Dr. Rainer Pöttgen Prof. Dr. 《无机化学与普通化学杂志》2007,633(10):1551-1555
The stannides ErAgSn and TmAgSn have been investigated under high‐temperature (HT) and high‐pressure (HP) conditions in order to investigate their structural chemistry. ErAgSn and TmAgSn are dimorphic: normal‐pressure (NP) ErAgSn and HT‐TmAgSn crystallize into the NdPtSb type structure, P63mc, a = 466.3(1), c = 729.0(2) pm for NP‐ErAgSn and a = 465.4(1), c = 726.6(2) pm for HT‐TmAgSn. NP‐ErAgSn was obtained via arc‐melting of the elements and subsequent annealing at 970 K, while HT‐TmAgSn crystallized directly from the melt by rapidly quenching the arc‐melted sample. HT‐TmAgSn transforms to the ZrNiAl type low‐temperature modification upon annealing at 970 K. The high‐pressure (HP) modification of ErAgSn was synthesized under multianvil high‐pressure (11.5 GPa) high‐temperature (1420 K) conditions from NP‐ErAgSn: ZrNiAl type, , a = 728.7(2), c = 445.6(1) pm. The silver and tin atoms in NP‐ErAgSn and HT‐TmAgSn build up two‐dimensional, puckered [Ag3Sn3] networks (277 pm intralayer Ag–Sn distance in NP‐ErAgSn) that are charge‐balanced and separated by the erbium and thulium atoms. The fourth neighbor in the adjacent layer has a longer Ag–Sn distance of 298 pm. The [AgSn] network in HP‐ErAgSn is three‐dimensional. Each silver atom has four tin neighbors (281–285 pm Ag–Sn). The [AgSn] network leaves distorted hexagonal channels, which are filled with the erbium atoms. The crystal chemistry of the three phases is discussed. 相似文献
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François P. Rotzinger PD Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(36):10298-10302
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Novel alkali trimolybdates of the triclinic (M, M′)2Mo3O10 (M = Rb; M′ = K, Cs) type were obtained through a systematic hydrothermal approach based on the reaction of MoO3 with alkali halide solutions at 180 °C. The crystal structures were determined from X‐ray single crystal data. The alkali trimolybdates extend the family of known alkali trimolybdates in an unexpected fashion, because they contain a distorted variation of [Mo3O10]2? chains as a key structural motif that has only been found in a single compound before, namely ethylenediammonium trimolybdate, (C2H10N2)[Mo3O10]. The applied hydrothermal strategy is discussed in the general context of systematic pathways to polyoxomolybdates. Furthermore, the templating role of the alkali cations and their interaction with the polyoxomolybdate surroundings is compared to (C2H10N2)[Mo3O10] in terms of electrostatic calculations. 相似文献
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Dennis Rottschäfer Beate Neumann Dr. Hans-Georg Stammler Dr. Ryohei Kishi Prof. Dr. Masayoshi Nakano PD Dr. Rajendra S. Ghadwal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3244-3247
Para-quinodimethane (pQDM) is a fundamental structural component in many π-conjugated organic molecules and materials. The incorporation of phosphorus atom into π-conjugated frameworks offers unique opportunities for controlling the properties of derived species. A phosphorus analogue of p-quinodimethane (pQDM), (IPrC)2P4 [ 5 , IPr=C{N(Ar)CH2}2; Ar=2,6-iPr2C6H3] featuring a planar P4 ring, was readily accessible by KC8-reduction of (IPrC)(PCl2)2 ( 2 ). Base-mediated C−H functionalization of IPrCH2 ( 1 ) with PCl3 afforded 2 . The formation of 5 was expected to occur through a dimerization of the transient 3H-diphosphirene (IPrC)P2 ( 4 ), which was theoretically suggested to have an intermediate diradical character. Compound 5 underwent photo-induced ring-contraction reaction to form the singlet diradicaloid (IPrCP)2 VI and white phosphorus (P4). The formation of and VI and P4 suggested the formal diphosphorus (P2) elimination from 5 . Indeed, photolysis of a mixture of 1,3-cyclohexadiene (CHD) and 5 led to the formation of P2-entrapped product (CHD)2P2 ( 6 ). The compound 5 represents the first organophosphorus species that functions as a P2 source. 相似文献