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Noonan KJ Feldscher B Bates JI Kingsley JJ Yam M Gates DP 《Dalton transactions (Cambridge, England : 2003)》2008,(33):4451-4457
The chemical functionality of poly(methylenephosphine) n-Bu[MesP-CPh(2)](n)H () is examined in reactions with two isoelectronic species, namely BH(3) and CH(3)(+). The potential reactivity of polymer is modelled by examining the reactivity of molecular phosphines bearing similar substituents as the polymer. In particular, the phosphine-borane adducts Mes(Me)P(BH(3))-CPh(2)H () and Mes(Me)P(BH(3))-CPh(2)SiMe(2)H () are prepared from the reaction of BH(3).SMe(2) with Mes(Me)P-CPh(2)H () or Mes(Me)P-CPh(2)SiMe(2)H (), respectively. Treating with MeOTf affords the methylated model compound, [Mes(Me)(2)P-CPh(2)H]OTf (). X-Ray crystal structures are reported for each model compound. The reaction of n-Bu[MesP-CPh(2)](n)H (M(n) = 3.89 x 10(4), PDI = 1.34) with BH(3).SMe(2) affords the phosphine-borane polymer n-Bu[MesP(BH(3))-CPh(2)](n)H () (M(n) = 4.13 x 10(4), PDI = 1.26). In contrast, methylation of phosphine polymer gives n-Bu[MesP-CPh(2)](x)-/-[MesP(Me)-CPh(2)](y)H.(OTf)(y) () where approximately 50% of the phosphine moieties are methylated (from (31)P NMR). 相似文献
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The Diels-Alder adducts of functionalized dienes with P-chloro-bis(trimethylsilyl)methylenephosphine can be aromatized, except in a few particular cases, thus opening a general route to functionalized phosphinines. The aromatization procedure differs with the substituents. Intermediates such as secondary cyclic phosphines could be characterized and even isolated. In some cases, aromatization and 1,5 sigmatropic shift of a trimethylsilyl group were observed and hydrogenolysis of the C Si bond as well. 相似文献
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Lauren E. Longobardi Dr. Timothy C. Johnstone Rosalyn L. Falconer Dr. Christopher A. Russell Prof. Dr. Douglas W. Stephan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12665-12669
The hydroboration of phosphaalkynes with Piers’ borane (HB(C6F5)2) generated unusual phosphaalkenylboranes [RCH=PB(C6F5)2]2 that persisted as dimers in both solution and the solid state. These P2B2 heterocycles underwent ring opening when subjected to nucleophiles, such as pyridine and tert‐butylisocyanide, to yield monomeric phosphaalkenylborane adducts RCH=PB(C6F5)2(L). DFT calculations were performed to probe the nature of the interaction of phosphaalkynes with boranes. 相似文献
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Yoshiki Chujo 《Macromolecular Symposia》1997,118(1):111-116
A polyaddition between diene and monoalkylborane produced a polymer consisting of C-B bonds in the main chain. The resulting organoboron polymers can be used as a novel type of reactive polymers. On the other hand, hydroboration polymerization of dicyano compounds produced air-stable poly(cyclodiborazane)s having B-N four-membered rings via dimerization of iminoborane species. Poly(organoboron halide)s were prepared either by haloboration polymerization between diynes and boron tribromide or by hydroboration polymerization of dienes with monobromoborane. Furthermore, phenylboration polymerization of diynes or diisocyanates gave new organoboron mainchain polymers. 相似文献
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Alternating phosphorus-carbon polymers are found to be effective ligands for gold(i) to afford [MesP(AuCl)-CPh2]n, a new class of macromolecule with high gold content. 相似文献
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Hydroboration of C(100) surface,fullerene, and the sidewalls of single-wall carbon nanotubes with borane 总被引:1,自引:0,他引:1
Hydroboration of three allotropes of carbon, i.e., diamond (100) surface, [60]fullerene, and single-wall carbon nanotubes (SWNTs), with borane (BH(3)) has been explored by means of quantum chemical calculations. The calculations predicted that the hydroboration of C(60) and the C(100)-2x1 surface occurs readily, whereas the hydroboration of the sidewall of an armchair (5,5) SWNT is thermoneutral with a barrier height of 11.5 kcal/mol. This suggests that sidewall hydroboration, if viable, would be highly reversible on the (5,5) SWNT. The as-hydroborated carbonous materials can be good starting points for further chemical modification and manipulation of these carbonous materials, given the abundant chemistry of organoboranes. 相似文献
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The changes in the chemical shifts of31P,13C, and29Si nuclei in structurally similar phosphaalkenes of the series XiP = C(SiMe3)2 have been investigated. The specific influence of the electrons of each of the four groups of substituents Xi on the delocalized -system –P = C(SiE, SiZ) has been revealed. When the effect of conjugation (or hyperconjugation) from Xi is strengthened, the screening of the SiZ atom increases as the SiE atom loses its screening. In the case of Xi with a predominant inductive effect (halogens, uncojugated groupings) the changes in the screening of SiZ and SiE are symbatic. The correlations of the chemical shifts a with Hammett's -constants and the behavior of the ionization potentials of the -and np energy levels in these compounds are discussed. It is assumed that the asymmetry in the degree of screening of the SiE and SiZ atoms is related to the participation of the unshared electron air of the P atom in the reaction with the –C(SiMe3)2 groupings.Institute of Organic Chemistry, Ukrainian Academy of Sciences, Kiev. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 6, pp. 703–710, November–December, 1991. Original article submitted May 21, 1990. 相似文献
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Kriti Pathak Sourav Gayen Suvam Saha Chandan Nandi Shivankan Mishra Prof. Dr. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(18):e202104393
Treatment of [Cp*RuCl2]2, 1 , [(COD)IrCl]2, 2 or [(p-cymene)RuCl2]2, 3 (Cp*=η5-C5Me5, COD= 1,5-cyclooctadiene and p-cymene=η6-iPrC6H4Me) with heterocyclic borate ligands [Na[(H3B)L], L1 and L2 ( L1 : L=amt, L2 : L=mp; amt=2-amino-5-mercapto-1,3,4-thiadiazole, mp=2-mercaptopyridine) led to the formation of borate complexes having uncommon coordination. For example, complexes 1 and 2 on reaction with L1 and L2 afforded dihydridoborate species [LAM(μ-H)2BHL] 4 – 6 ( 4 : LA=Cp*, M=Ru, L=amt; 5 : LA=Cp*, M=Ru, L=mp; 6 : LA=COD, M=Ir, L=mp). On the other hand, treatment of 3 with L2 yielded cis- and trans-bis(dihydridoborate) species, [Ru{(μ-H)2BH(mp)}2], cis- 7 and trans- 7 . The isolation and structural characterization of fac- and mer-[Ru{(μ-H)2BH(mp)}{(μ-H)BH(mp)2}], 8 from the same reaction offered an insight into the behaviour of these dihydridoborate species in solution. Fascinatingly, despite having reduced natural charges on Ru centres both at cis-and trans- 7 , they underwent hydroboration reaction with alkynes that yielded both Markovnikov and anti-Markovnikov addition products, 10 a – d . 相似文献
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硅卡宾(R2Si:,silylene)是卡宾的相似体,可以作为配体与金属形成配合物.由于硅的原子半径比碳大,硅卡宾可与Lewis碱配位形成三配位甚至四配位的化合物同时保持很强的配位能力.因此,硅卡宾兼具卡宾和膦配体的结构特征,在稳定新颖的金属配合物及均相催化领域或具有更大的调控空间.本工作报道硅卡宾铁氮气配合物[PhC (t-BuN)2SiCH2C (t-Bu) NAr]FeN2(D,Ar=2,6-(i-Pr)2C6H3)催化的炔烃的选择性硼氢化反应.研究发现,该配合物对炔烃的硼氢化反应具有很好的区域及立体选择性,主要生成E式构型产物并表现出很好的官能团耐受性.该研究表明,硅卡宾对过渡金属催化具有很好的调控作用,具有很好的研究潜力. 相似文献
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Maude Aelterman Dr. Morgane Sayes Prof. Dr. Philippe Jubault Prof. Dr. Thomas Poisson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(32):8277-8282
Herein we reported the electrochemical hydroboration of alkynes by using B2Pin2 as the boron source. This unprecedented reaction manifold was applied to a broad range of alkynes, giving the hydroboration products in good to excellent yields without the need of a metal catalyst or a hydride source. This transformation relied on the possible electrochemical oxidation of an in situ formed borate. This anodic oxidation performed in an undivided cell allowed the formation of a putative boryl radical, which reacted on the alkyne. 相似文献
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Yoshiyuki Nagashima Keiji Sasaki Takahiro Suto Prof. Dr. Takaaki Sato Prof. Dr. Noritaka Chida 《化学:亚洲杂志》2018,13(8):1024-1028
Full details of a stereodivergent hydroboration of allenes are reported. While hydroboration of an allene with 9‐BBN provided a thermodynamically stable (E)‐allylic alcohol after oxidative work‐up, the reaction of an identical allene with HB(Sia)2 (disiamylborane) formed a (Z)‐allylic alcohol as the kinetic product. The developed conditions allowed for the synthesis of trisubstituted olefins in a highly stereoselective fashion, which is known to be challenging. The method was also applied to the stereodivergent synthesis of structural motifs such as skipped dienes and allylbenzenes, which are often embedded in biologically active natural products. 相似文献
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Rajrani Narvariya Dr. Suman Das Susmita Mandal Dr. Archana Jain Prof. Tarun K. Panda 《欧洲无机化学杂志》2023,26(25):e202300247
We report catalytic hydroboration of esters as well as nitriles under solvent-free and mild conditions using single titanium(IV) metal complex, [{κ2-C6H4C(O)N(iPr)C(N-iPr)=N}{κ3-(iPr)N=C(O)−C6H4−NC(NMe2)N(iPr)}TiNMe2] 1 as a sustainable, economical, and efficient pre-catalyst. The molecular structure of the TiIV complex in the solid state reveals the unique coordination of TiIV metal with N, N, and O atoms of one quinazolinone unit via in-situ rearrangement, while another quinazolinone moiety coordinates in bidentate fashion via both N atoms only. The TiIV complex demonstrates excellent activity as a pre-catalyst towards the hydroboration of a wide array of esters and nitriles with pinacolborane (HBpin) to afford alkoxyboranes and diboryl amines in high yield (up to 99 %) with greater tolerance to a variety of electron-withdrawing and electron-donating functional groups. A most plausible mechanism of hydroboration of esters is also proposed based on kinetics and NMR studies, which suggests the formation of titanium-hydride species as an active catalyst. 相似文献
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Capturing HBCy2: Using N,O‐Chelated Complexes of Rhodium(I) and Iridium(I) for Chemoselective Hydroboration
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Marcus W. Drover Prof. Dr. Laurel L. Schafer Prof. Dr. Jennifer A. Love 《Angewandte Chemie (International ed. in English)》2016,55(9):3181-3186
1,3‐N,O‐chelated complexes of RhI and IrI cooperatively and reversibly stabilized the B?H bond of HBCy2 to afford six‐membered metallaheterocycles (M=Rh ( 7 ) or Ir ( 8 )) having a δ‐[M]???H‐B agostic interaction. Treatment of these Shimoi‐type borane adducts 7 or 8 with both an aldehyde and an alkene resulted in chemoselective aldehyde hydroboration and reformation of the 1,3‐N,O‐chelated starting material. The observed chemoselectivity is inverted from that of free HBCy2, which is selective for alkene hydroboration. 相似文献