Comparative Study of the Phospha- and Arsa-Wittig Reaction Using1H,75As and17O NMR Spectroscopy
作者:Christian Raeck、Stefan Berger
DOI:10.1002/ejoc.200600432
日期:2006.11
The existence of oxaarsetanes during an arsa-Wittigreaction has been proved by 1 H and 17 O NMRspectroscopy. 75 As NMR spectra were obtained from the corresponding arsonium salts and arsane oxides. The dynamic 1 H NMR spectra of phospha- and arsaylides were compared.
已通过 1 H 和 17 O NMR 光谱证明了在 arsa-Wittig 反应过程中存在氧杂亚锡烷。75 As NMR 光谱是从相应的砷盐和砷烷氧化物中获得的。比较了磷和亚砷酸内酯的动态 1 H NMR 谱。
Polymeric complexes from molybdenum trioxide, with notes on derivatives and related compounds
作者:Richard N. Hider、Cuthbert J. Wilkins
DOI:10.1039/dt9840000495
日期:——
from which the polymeric complex [MoO3(dmso)1.33}n](1a) may be crystallised. It also reacts with pyridine N-oxide (pyo), triphenylarsine oxide, and pyridine (py) to give insoluble polymeric complexes [MoO3(pyo)}n](2), [MoO3(AsPh3O)0.5}n](3), and [MoO3(py)}n](4). The solubility of (1a) enables its conversion to (2), (3), or (4). Another compound, [MoO3(AsPh3O)}n](5) has been obtained from the MoVI
三氧化钼溶于二甲基亚砜(dmso),得到一种溶液,从中可以结晶出聚合物络合物[MoO 3(dmso)1.33 } n ](1a)。它还与吡啶N-氧化物(pyo),三苯基ar氧化物和吡啶(py)反应,生成不溶的聚合物络合物[MoO 3(pyo)} n ](2),[MoO 3(AsPh 3 O)0.5 } n ](3)和[MoO 3(py)} n ](4)。(1a)的溶解度使其能够转化为(2),(3)或(4)。另一种化合物[MoO 3(AsPh 3 O)} n](5)是从Mo VI乙酰丙酮络合物[MoO 2(acac)2 ]获得的。关于不溶性化合物组成的证据来自红外光谱和X射线衍射图,以及“白色”和“黄色”钼酸[[MoO 3(OH 2)} n ]和[MoO 3(OH 2)] } n ]· n H 2O分别提供参考结构。钼配位环境包括与单个末端氧相对的配体以及四个桥联原子,如酸的黄色
Deoxygenative Fluorination of Phosphine Oxides: A General Route to Fluorinated Organophosphorus(V) Compounds and Beyond
Fluorinated organophosphorus(V) compounds are a very versatile class of compounds, but the synthetic methods available to make them bear the disadvantages of 1) occasional handling of toxic or pyrophoric PIII starting materials and 2) a dependence on hazardous fluorinating reagents such as XeF2. Herein, we present a simple solution and introduce a deoxygenative fluorination (DOF) approach that utilizes
Synthesis, structure, and reactivity of (tropon-2-ylimino)arsorane and in situ generation of its stiborane and bismuthorane analogues: reactions with heterocumulenes and an activated acetylene giving heteroazulenes
作者:Makoto Nitta、Yuhki Mitsumoto、Hiroyuki Yamamoto
DOI:10.1039/b103098c
日期:——
(Tropon-2-ylimino)pnictoranes of the general structure RNMPh3 (R = tropon-2-yl; M = As, Sb, and Bi) 4–6 have been prepared for the first time by the reaction of 2-aminotropone with Ph3MX2 (M = As, Sb, and Bi) in the presence of a base. The arsorane derivative (M = As) 4 is isolated as a stable crystalline compound, while the stiborane (M = Sb) and the bismuthorane (M = Bi) derivatives 5 and 6 are not isolated and are
σ-Bonded early transition metal–carbon derivatives. Part III. Complexes of methyltungsten(<scp>VI</scp>) pentahalide, halide oxide, and halide dioxide
作者:Catherine Santini-Scampucci、Jean G. Riess
DOI:10.1039/dt9760000195
日期:——
Methyltungsten(VI) pentachloride has been obtained from WCl6 with HgMe2, and characterised by n.m.r. and i.r. spectroscopy. Reactions of WMeCl5 with bidentate ligands give WMeCl5·L adducts L = Ph2P[CH2]2PPh2 or O[OP(NMe2)2]2}, while unidentate ligands give either extensive reduction [MeCN, SO(OMe)2, PO(OMe)3, or P(NMe2)3O] or chlorine–oxygen exchange reactions to WMeCl3O·L or WMeClO2·2L compounds