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The coordination of silver cation to diphosphene Mes*P=PMes* ( 1 , Mes* = tBu3C6H2) was investigated in detail. The reaction of 1 with Ag[Al(ORF)4] (ORF = OC(CF3)3) in the ratios of 2 : 1, 3 : 2 and 1 : 2 led to the formation of the first cationic silver linked diphosphene complexes 2 — 4 . Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(I) cation, respectively, and they feature unusual zig‐zag topologies. Complex 4 is a dinuclear silver complex, and each Ag(I) center features a tetrahedral geometry, coordinated by one phosphorus atom of diphosphene 1 and three chloro atoms of two CH2Cl2 molecules. 相似文献
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Masaaki Yoshifuji 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1827-1831
Low-coordinate organophosphorus compounds can be prepared by steric protection. They are diphosphenes, phosphaethenes, phosphaallenes, phosphabutatrienes, phosphaalkynes, and so on, of coordination number 2 and 1 . 相似文献
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Naoki Hayakawa Kazuya Sadamori Shota Tsujimoto Prof. Dr. Miho Hatanaka Prof. Dr. Tomonari Wakabayashi Prof. Dr. Tsukasa Matsuo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(21):5859-5863
The reaction of the bulky diphosphenes (Rind)P=P(Rind) ( 1 ; Rind=1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacen-4-yl) with two molecules of N-heterocyclic carbene (NHC; 1,3,4,5-tetramethylimidazol-2-ylidene) resulted in the quantitative formation of the NHC-bound phosphinidenes NHC→P(Rind) ( 2 ), along with the cleavage of the P=P double bond. The reaction times are dependent on the steric size of the Rind groups (11 days for 2 a (R=Et) and 2 h for 2 b (R=Et, Me) at room temperature). The mechanism for the double bond-breaking is proposed to proceed via the formation of the NHC-coordinated, highly polarized diphospehenes 3 as an intermediate. Approach of a second NHC to 3 induces P−P bond cleavage and P−C bond formation, which proceeds through a transition state with a large negative Gibbs energy change to afford the two molecules of 2 , thus being the rate-determining step of the overall reaction with the activation barriers of 80.4 for 2 a and 29.1 kJ mol−1 for 2 b . 相似文献
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Andreas Orthaber 《Journal of organometallic chemistry》2010,695(7):974-980
The reactivity of a series of phosphanes with a fluoroaryl group (HF4C6-) carrying a spectator function in para position has been explored with respect to the formation of low coordinated and phosphorus rich phosphanes. An asymmetric diphosphene has been indentified as an intermediate in the synthesis of a linear 1,3-dihydrophosphane, while the symmetric diphosphene undergoes 2 + 2 cycloaddition under formation of the corresponding cyclotetraphosphetane for which a crystal structure could be obtained. Attempts to synthesize HF4C6-substituted iminophosphanes generally failed, which is attributed to the electronic nature of the corresponding precursors as suggested by quantum chemical calculations. 相似文献
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Norihiro Tokitoh Takahiro Sasamori Nobuhiro Takeda Shigeru Nagase 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1473-1476
The first stable phosphabismuthene (R 1 --P=Bi--R 2 ) and stibabismuthene (R 1 --Sb=Bi--R 2 ) were successfully synthesized by taking advantage of efficient steric protection groups, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt), 2,6-bis[bis(trimethylsilyl)-methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt), and 2,4,6-tri- t -butylphenyl (Mes*). Their spectroscopic properties and structural parameters were systematically compared with those of previously reported stable, homonuclear, doubly bonded systems, such as diphosphene, diarsene, distibene, and dibismuthene. 相似文献
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Shun‐suke Asami Masafumi Okamoto Katsunori Suzuki Makoto Yamashita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(41):13019-13023
A boryl‐substituted diphosphene was synthesized through the nucleophilic borylation of PCl3 with a borylzinc reagent, followed by a reduction with Mg. A combined analysis of the resulting diboryldiphosphene by single‐crystal X‐ray diffraction, DFT calculations, and UV/Vis spectroscopy revealed a σ‐electron‐donating effect for the boryl substituent that was slightly weaker than that of the 2,4,6‐tri‐tert‐butylphenyl (Mes*) ligand. The reaction of this diboryldiphosphene with nBuLi afforded a boryl‐substituted phosphinophosphide that was, in comparison with the thermally unstable Mes*‐substituted diaryldiphosphene, stabilized by a π‐electron‐accepting effect of the boryl substituent. 相似文献
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Noriyoshi Nagahora Takahiro Sasamori Yukio Furukawa 《Journal of organometallic chemistry》2008,693(4):625-632
The stable lithium diphosphene anion radical, [Li(dme)3]+[TbtPPTbt]− (dme: 1,2-dimethoxyethane, Tbt: 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl), was readily synthesized by the one-electron reduction of the corresponding neutral diphosphene (TbtPPTbt). The molecular structure of the diphosphene anion radical was discussed in detail on the basis of its ESR, UV-Vis and Raman spectra, and theoretical calculations. The diphosphene anion radical was found to undergo ready chalcogenation reactions using elemental sulfur and selenium to afford the corresponding thiadiphosphirane and selenadiphosphirane, respectively. 相似文献
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1,3-Bis(triphenylphosphonium-ylidyl)cyclotetraphosphines The title compounds 3a , b result from the condensation of the ylidyldichlorophosphines Ph3PCR? PCl2 1a , b (R = Me, 3-Tol) with phenyl bis(trimethylsilyl)phosphine 2 . Analysis of the 31P-NMR spectra and the X-ray structure investigation of 3a demonstrate a folding of the four-membered ring and an all-trans orientation of the substituents. 相似文献