Synthesis and Crystal Structure of[(2 , 4-Me_2C_5H_5)_2NdC ＝CC_6H_5]_2

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［（２，４－Ｍｅ＿２Ｃ＿５Ｈ＿５）＿２ＮｄＣ＝ＣＣ＿６Ｈ＿５］＿２ＺＨＡＮＧＳｕｏ－ｂｏａｎｄＬＩＵＪｕ－ｚｈｅｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＪｉｌｉｎＵｎｉｖｅｒｓｉｔ...     

Studies on the Reactivities of Undecatungstogallates K＿n［GaW＿（11）O＿（39）M（H＿2O）］·xH＿2O（M＝Mn，Co，Ni，Cu，Cr，FeorZn）

ＳｔｕｄｉｅｓｏｎｔｈｅＲｅａｃｔｉｖｉｔｉｅｓｏｆＵｎｄｅｃａｔｕｎｇｓｔｏｇａｌｌａｔｅｓＫ＿ｎ［ＧａＷ＿（１１）Ｏ＿（３９）Ｍ（Ｈ＿２Ｏ）］·ｘＨ＿２Ｏ（Ｍ＝Ｍｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ｃｒ，ＦｅｏｒＺｎ）ＬＩＵＪｉｎｇ－ｆｕ，ＺＨＡＮＸｉａｏ－ｐ...     

Synthesis and Structure of Ion-pairComplex［Mo （dtc）_4］［Sm （dtc）_4］

ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃｔｕｒｅｏｆＩｏｎ－ｐａｉｒＣｏｍｐｌｅｘ［Ｍｏ（ｄｔｃ）＿４］［Ｓｍ（ｄｔｃ）＿４］ＳＵＮＣｈｕｎ－ｔｉｎｇ，ＺＨＵＹａ－ｂｉｎ，ＬＩＵＸｉａｏ－ｘｕｎａｎｄＹＩＳｈｕｚｈｅｎ（ＣｈｅｍｉｓｔｒｙＤｅｐａｒｔｍｅｎ...     

(η~2C_(60))Pt (PPh_3)_2 as the Catalystfor the Hydrosilylation of Olefins

（η￣２Ｃ＿（６０））Ｐｔ（ＰＰｈ＿３）＿２ａｓｔｈｅＣａｔａｌｙｓｔｆｏｒｔｈｅＨｙｄｒｏｓｉｌｙｌａｔｉｏｎｏｆＯｌｅｆｉｎｓＣＨＥＮＹｕａｎ－ｙｉｎ,ＳＨＥＮＧＲｏｎｇ－ｓｈｅｎａｎｄＬＩＵＹｉｎｇ（ＤｅｐａｒｔｒｎｅｎｔｏｆＣｈｅｒｎｉｓｔｒ...     

Synthesis and ￣（183）W NMR Characterization of β－［（CeO）＿3（SiW＿9O＿（34））＿2］￣（14－） Heteropolyanion

Ｓｙｎｔｈｅｓｉｓａｎｄ￣（１８３）ＷＮＭＲＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆβ－［（ＣｅＯ）＿３（ＳｉＷ＿９Ｏ＿（３４））＿２］￣（１４－）ＨｅｔｅｒｏｐｏｌｙａｎｉｏｎＭＥＮＧＬｕａｎｄＬＩＵＪｉｎｇ－ｆｕ（ＤｅｐａｒｔｎｉｅｎｔｏｆＣｈｅｍｉ...     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF NdBr_3(i-C_3H_7OH)_2(THF)_2

ＴＨＥ　ＳＹＮＴＨＥＳＩＳ　ＡＮＤ　ＣＲＹＳＴＡＬ　ＳＴＲＵＣＴＵＲＥ　ＯＦ　ＮｄＢｒ＿３（ｉ－Ｃ＿３Ｈ＿７ＯＨ）＿２（ＴＨＦ）＿２￥ＨｏｎｇＹｅＳＵＮ；ＣｈｕｎＨｕｉＨＵＡＮＧａｎｄＧｕａｎｇＸｉａｎＸＵ（ＲｅｓｅａｒｃｈＣｅｎｔｅｒｏｆＲａｒｅＥ...     

Synthesis and Crystal Structural Characterization of （NH＿4）＿5H＿3Mn＿3V＿（12）O＿（40）·15H＿2O

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒａｌＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆ（ＮＨ＿４）＿５Ｈ＿３Ｍｎ＿３Ｖ＿（１２）Ｏ＿（４０）·１５Ｈ＿２ＯＷＡＮＧＺｕｏ－Ｐｉｎｇ;ＬＩＵＪｉｎｇ－ｆｕａｎｄＷＡＮＧＥｎ－ｂｏ（Ｄｅｐａｔｍｅｎ...     

INDOStudiesonElectronicStructuresof（C＿8H＿8）Ln（2，4－C＿4H＿11）（THF）（Ln＝Nd，Sm，Er）

ＩＮＤＯＳｔｕｄｉｅｓｏｎＥｌｅｃｔｒｏｎｉｃＳｔｒｕｃｔｕｒｅｓｏｆ（Ｃ＿８Ｈ＿８）Ｌｎ（２,４－Ｃ＿４Ｈ＿１１）（ＴＨＦ）（Ｌｎ＝Ｎｄ,Ｓｍ,Ｅｒ）ＷＡＮＧＺｈｉ－ｚｈｏｎｇ＊,ＦＥＮＧＪｉａｎ－ｎａｎ,ＺＨＡＮＧＳｏ－ｂｏａｎｄＬＩＵＪｕ－ｚｈ...     

EHMO Studies of Chemisorbed Dioxygen Species on Na＿2O and K＿2O and of Their Interaction with CH＿4 and CH＿3－Radical

ＥＨＭＯＳｔｕｄｉｅｓｏｆＣｈｅｍｉｓｏｒｂｅｄＤｉｏｘｙｇｅｎＳｐｅｃｉｅｓｏｎＮａ＿２ＯａｎｄＫ＿２ＯａｎｄｏｆＴｈｅｉｒＩｎｔｅｒａｃｔｉｏｎｗｉｔｈＣＨ＿４ａｎｄＣＨ＿３－ＲａｄｉｃａｌＳＵＱｉａｏ－Ｊｕａｎ,ＺＨＡＮＧＨｏｎｇ－ｂｉｎ,ＺＨ...     

SYNTHESIS OF CF_3-SUBSTITUTED ENEDIYNES

ＳＹＮＴＨＥＳＩＳＯＦＣＦ＿３－ＳＵＢＳＴＩＴＵＴＥＤＥＮＥＤＩＹＮＥＳＳＹＮＴＨＥＳＩＳＯＦＣＦ＿３－ＳＵＢＳＴＩＴＵＴＥＤＥＮＥＤＩＹＮＥＳ￥ＦｅｎｇＨＯＮＧａｎｄＣｈａｎｇＭｉｎｇＨＵ（ＳｈａｎｇｈａｉＩｎｓｔｉｔｕｔｅｏｆＯｒｇａｎｉｃＣｈｅ...     

Hydrothermal Deoxygenation of Graphene Oxide: Chemical and Structural Evolution

A green and facile approach for the partial deoxygenation of graphene oxide (GO) at moderate temperature (100 °C) and under atmospheric pressure, catalyzed by acidic conditions in water is reported. The chemical and structural changes in GO as a function of hydrothermal time were probed to understand the deoxygenation events. The brown GO dispersion in water was found to gradually turn black over the hydrothermal‐treatment time on account of the increasing graphitic content. FTIR, thermogravimetric (TG), Raman, and XRD analyses revealed that the labile oxygen functionalities are progressively eliminated, thereby partially restoring the π‐conjugated network. This was further corroborated by X‐ray photoelectron spectroscopy (XPS) studies based on quantitative analysis of each carbon component associated with the different chemical functionalities. Carbonyl, carboxyl, ether, and phenolic groups were found to be thermally stable, which hinders complete deoxygenation of GO and makes their dispersion in water stable, as monitored by the ζ potential. It is worth noting that deoxygenation events are expedited under acid‐catalyzed hydrothermal treatment relative to thermal deoxygenation in air.     

Radical deoxygenation of hydroxyl groups via phosphites

A highly efficient, two-step sequence method for the deoxygenation of hydroxyl groups has been developed. The method involves the preparation of the 2-(2-iodophenyl)ethyl methyl phosphite derivative of an alcohol using methyl dichlorophosphite and 2-(2-iodophenyl)ethanol. Treatment of the phosphite intermediate with (n-Bu)3SnH/AIBN in refluxing benzene cleanly produces the deoxygenation product of the original alcohol.     

Cu-Ce/γ-Al2O3对硬脂酸催化水热脱氧产生烷烃的效果

利用等体积浸渍法制备Cu-Ce/γ-Al₂O₃催化剂，并在无H₂存在的条件下对硬脂酸进行催化水热液化。对催化剂进行BET比表面积分析和X射线衍射（XRD）分析可知，Cu-Ce/γ-Al₂O₃催化剂中存在CuO和CeO₂两种晶型，在300℃条件下水热反应12 h后具有更好的热稳定性。通过对硬脂酸进行水热液化实验和对生物油进行气相色谱-质谱（GC-MS）分析发现，加入Cu-Ce/γ-Al₂O₃催化剂能够获得最高的硬脂酸转化率（94.71%）和总烃产率（81.41%），水热液化脱氧效果最好。分析正烷烃的产率，结果发现硬脂酸在高温水热条件下主要发生脱羧反应。Cu-Ce/γ-Al₂O₃催化剂的加入能够同时促进反应过程中脱羧反应、加氢脱氧反应和裂化反应。此外，Cu-Ce/γ-Al₂O₃还能够促进羰基基团的脱除，有效减少产物中的醛和酮类物质。     

Catalytic activity of iron hydroxides and manganese hydroxides in the deoxygenation of water

Catalysts prepared by the modification of FIBAN K-4 and FIBAN X-1 fibrous ion exchangers with the hydroxides of iron and manganese were developed and tested in a water deoxygenation process. It was established that the samples obtained by the supporting of Fe(III) hydroxide onto the FIBAN X-1 ampholyte were most effective. The conclusion that the high activity of the catalytic system is caused by the formation of a mixed phase of Fe(II) and Fe(III) hydroxides of the spinel type containing mobile (weakly bound) lattice oxygen was made. A reaction scheme was proposed to explain the reaction mechanism.     

The interaction of pentacarbonyl iron(O) with selected 1,2-quinone mono-oximes (2-nitrosophenols) in the presence or absence of aniline

Reaction of pentacarbonyl iron(O) with 1,2-quinone mono-oximes (qoH) gives the Fe(qO)₂ complexes as the main products together with various organic products. In the presence of aniline the main products are again the complexes Fe(qO)₂ which are accompanied by the formation of organic products and complexes of type Fe(qo-A)₂ where qo-A is a species arising from the coupling of the qo ligand with aniline. The formation of the latter type of complex and of the organic products is rationalized in terms of deoxygenation of the qo ligand. The complexes Fe(qo)₂ and Fe(qo-A)₂ have oligomeric structures as indicated by their magnetic properties and Mössbauer spectra. Both these types of complex react with pyridine to give dipyridine adducts.     

Ni基双金属催化剂加氢脱氧性能的研究

考察了Ni-M/γ-Al2O3（M＝Co、Cu、Fe、La）双金属催化剂对醇、酸、酮有机含氧化合物（丁醇、丁酸、丁酮）的加氢脱氧性能,并对其中间产物进行了考察。通过TPR、XRD表征手段对Ni基催化剂的还原性能、表面分散度等特性进行了研究。结果表明,Ni基催化剂中第二活性组分相对不同有机含氧化合物表现出不同的加氢活性和选择性。对于丁酸,在Ni基催化剂中加入Fe表现出较好的活性;对于丁醇,加入La有较好的加氢脱氧性能;而对于丁酮,加入Cu更有利于提高催化剂的脱除性能。醇和酯是有机酸在Ni/γ-Al2O3催化剂上加氢转化的中间产物。     

Photoinduced oxygen dynamics in lyophilized hemoglobin

Reversible laser induced deoxygenation in the lyophilized phase of hemoglobin is demonstrated by means of resonant Raman scattering, luminescence, and optical transmission. Specific Raman modes, which are both sensitive to the spin states of Fe(II) in the hemes and resonant in the visible, are monitored as a function of time to evaluate the effect of the illuminating laser. These modes act as in-situ markers of the oxygen content of the protein. The reversible photoinduced deoxygenation can be observed through both the Raman spin-markers and the optical transmission experiments. In the former, reversible changes in the intensities of specific Raman modes are observed, while in the latter, the oscillator strength of the two main absorptions of oxyhemoglobin in the visible are seen to vary accordingly. The luminescence in lyophilized hemoglobin is found to have at least two different contributions, (i) a resonant component with the Raman modes and; (ii) a nonresonant contribution, which increases at high input laser powers and eventually masks the Raman signals. The nonresonant contribution is the luminescence of the photoproduct achieved by thermal denaturation of the protein and remains standing as a permanent nonreversible damage in the illuminated spot. Semiempirical electronic calculations of the wavefunction and total energy of the iron porphyrin reveal the underlying physical origin of the laser induced deoxygenation process in the hemes and are also presented.     

Iron-catalyzed deoxygenation and 2-sulfonylation of quinoline N-oxides by sodium sulfinates towards 2-sulfonyl quinolines

An iron(III)-catalyzed protocol towards 2-sulfonyl quinolines from quinoline N-oxides and sodium sulfinates was herein illustrated. The general and direct option featured for high efficiency (up to 91% yields) and good functional compatibilities (27 examples) in the Fe(III)-catalysis. Moreover, free radical mechanism was proposed for the one-pot deoxygenation and sulfonylation reaction based on the results of the control reactions.     

Lewis acid-promoted electron transfer deoxygenation of epoxides, sulfoxides, and amine N-oxides: the role of low-valent niobium complexes from NbCl5 and Zn

A mild and operationally simple deoxygenation of epoxides, sulfoxides, and amine N-oxides is described using a sub-stoichiometric amount of low-valent niobium complexes generated in situ from commercially available NbCl₅ and zinc dust. The deoxygenation proceeds by a reductive cleavage of polarized O-C/O-N/O-S bonds through a single electron transfer from zinc metal to the niobium-substrate complex due to the high oxophilic nature of the niobium species. The presence of adjacent radical-stabilizing groups is beneficial to epoxide substrates; however the similar prerequisite does not apply to sulfoxides and amine N-oxides, where a broad range of substrates are efficiently deoxygenated in excellent yields.     

Novel deoxygenation reaction of epoxides by indium

[reaction: see text] A novel, mild, ecofriendly protocol for the deoxygenation of epoxides to alkenes using indium metal and indium(I) chloride or ammonium chloride in alcohol has been developed. It was necessary for the presence of good radical-stabilizing groups adjacent to the oxirane ring for the deoxygenation reaction to occur. It is proposed that this reaction occurs through an SET process with indium as an electron donor.