本文证明,构成自组装单层 (SAM) 的分子的分子构象(除了组成和结构外)影响通过它们的电荷隧穿 (CT) 速率,在形式为 Au TS / S( CH 2 ) 2 CONR 1 R 2 //Ga 2 O 3 /EGaIn,其中R 1和R 2是不同长度的烷基链。链的长度 R 1和 R 2选择影响单层中分子的构象和构象均匀性。分子的构象影响单层的厚度(即隧道势垒宽度)及其在±1.0 V 时的整流比。当R 1 = H 时,分子有序且主要以反式扩展构象存在。然而,当R 1是烷基(例如,R 1 ≠H)时,它们的构象不再是全反式延伸的,并且分子采用更多的斜切二面角。构象类型的这种变化降低了构象顺序并影响隧穿速率。当 R 1 = R 2,当 R 1 = H 时,相对于通过具有相同总链长或厚度的 SAM 观察到的 CT 速率,CT 速率降低(高达 6.3 倍)。当 R 1 ≠ H ≠ R 2 时,存在较弱
A system of potassium metal-crown ether-diglyme has been proved to be highly effective for reductive removal of the sulfonyl group from O-sulfonates or sulfonamides. The reaction proceeds even with mesylamides of dialkyl amines, which resist reductive cleavage by naphthalene radical anion. It has also been found that a simple combination of potassium metal or sodium-potassium alloy with isopropanol in diglyme or toluene is effective for the cleavage of dialkylamine sulfonamides which are relatively susceptible to reduction. In particular, the use of sodium-potassium alloy gave satisfactory results.
Direct Access to POP-Type Osmium(II) and Osmium(IV) Complexes: Osmium a Promising Alternative to Ruthenium for the Synthesis of Imines from Alcohols and Amines
作者:Miguel A. Esteruelas、Nicole Honczek、Montserrat Oliván、Enrique Oñate、Marta Valencia
DOI:10.1021/om200290u
日期:2011.5.9
easy and direct access to POP-type osmium(II) and osmium(IV) complexes, including OsH4dbf(PiPr2)2} (dbf(PiPr2)2 = 4,6-bis(diisopropylphosphine)dibenzofuran), is reported. This tetrahydride derivative is an efficient catalyst for the selective formation of imines fromalcohols and amines with liberation of H2, proving that osmium is a promising alternative to ruthenium for catalysis.
轻松直接访问POP型(II)和(IV)络合物,包括OsH 4 dbf(P i Pr 2)2 }(dbf(P i Pr 2)2 = 4,6-双(二异丙基膦) )二苯并呋喃)。该四氢化物衍生物是从醇和胺中选择性释放出H 2选择性地形成亚胺的有效催化剂,证明是钌的理想替代催化剂。
Palladium catalyzed N-alkylation of amines with alcohols
作者:Yan Zhang、Xiujuan Qi、Xinjiang Cui、Feng Shi、Youquan Deng
DOI:10.1016/j.tetlet.2011.01.059
日期:2011.3
An iron oxide immobilized palladium catalyst was prepared for the N-alkylation of amines with alcohols under base and organic ligand free conditions. Applying the optimized reaction conditions, the coupling reactions of amines and alcohols with various structures could be realized with up to 99% isolated yields. The catalysts were studied by XRD, BET, and XPS and the mechanism was studied by DFT calculations
That's just silyl! Selective nickel‐catalyzed reductiveamination of aldehydes under hydrosilylation conditions is achieved by using a one pot, two step procedure. By using an in situ‐generated catalyst (5 mol %) from Ni(OAc)2 and tricyclohexylphosphine with tetramethyldisiloxane (TMDS) as the hydrosilane at 70 °C, the corresponding secondary amines were obtained in moderate to good isolated yields
There is disclosed a lubricating oil composition containing a dual additive combination for reducing the low temperature viscosity properties thereof. Such additive combination comprises a polymethacrylate or esterified styrene/maleic anhydride copolymer and a sorbitan tristearate.