介绍了几种具有双(烯烃)-氨基配体的零价钴配合物的合成和表征。这些络合物中的某些被证明是即使具有直接的P-P键也能选择性氧化仲和烯丙基膦以及二膦的有效催化剂。催化剂负载量为5 mol%时,氧化会在温和的条件下(25–70°C,7–22 h,2 bar N 2 O)进行,并提供良好至极好的收率(65–98%)。在此过程中,温室气体N 2 O被催化转化为良性N 2和增值有机磷化合物,其中一些很难以其他方式获得。
我们对具有不同取代基的二膦烷的合成,结构和性质进行了全面的研究。为此,我们合成了一系列新颖的通式为R 1 R 2 P-PR 3 R 4的烷基,芳基和氨基取代的二膦(其中R 1,R 2,R 3,R 4 = t Bu ,Ph,Et 2 N或iPr 2 N)通过卤代膦与金属磷化物的盐复分解反应,收率很高。通过获得第一个被单氨基和三氨基取代的系统,我们极大地扩展了这类化合物的范围。分离的化合物的结构通过NMR光谱和X射线衍射表征。分离出的不对称二膦烷没有重新排列为相应对称物质的趋势。此外,我们根据与磷原子连接的不同基团的数量及其在分子中的分布,提出了二膦的一般分类。为了研究取代基对P中心和整个分子的性质的影响,我们对获得的系统的电子和空间性质进行了DFT研究。
Versatile behaviour of the phosphanyl salt (Pri 2N)2 P+CF3SO3 ? towards zirconocene derivatives
作者:Florence Boutonnet、Maria Zablocka、Alain Igau、Jean-Pierre Majoral、Jo�l Jaud、Kazimierz M. Pietrusiewicz
DOI:10.1039/c39930001487
日期:——
Transfer reactions of various groups (Ph2P[CH2]3â, Ph2CCPhâCHNâ, N3, CN, Me, Cl, H) occurred from zirconium to phosphorus in reactions of the phosphanylium salt (Pri2N)2 P+CF3SO3â with zirconocene derivatives; the crystal structure of (Pri2N)2PâCHNâP(NPri2)28 has been determined.
1,1-diamino-2,2-diphenyl-substituted diphosphines featuring various degrees of P-P bond polarization with different alkynes were investigated. All diphosphines reacted with alkynes carrying one or two electron withdrawing carboxylic ester moieties under cleavage of the P-P bond and stereospecific phosphinyl-phosphination at the triple bond to give unsymmetrical ethane-1,2- bisphosphines. Several of
Exploring the Reactivity of Unsymmetrical Diphosphanes toward Heterocumulenes: Access to Phosphanyl and Phosphoryl Derivatives of Amides, Imines, and Iminoamides
phenyl thioisocyanate gave rise to phosphanyl, phosphoryl, and thiophosphorylderivatives of amides, imines, and iminoamides. The structures of the diphosphanation products were confirmed through NMR spectroscopy, IR spectroscopy, and single-crystal X-ray diffraction. We showed that unsymmetrical diphosphanes could be used as buildingblocks to synthesize phosphorus analogues of important classes of organic
我们对不对称二膦对异(硫)氰酸酯的二膦化进行了综合研究。涉及不对称二膦和异氰酸苯酯或硫代异氰酸苯酯的反应产生酰胺、亚胺和亚氨基酰胺的磷酰基、磷酰基和硫代磷酰基衍生物。通过 NMR 光谱、IR 光谱和单晶 X 射线衍射证实了二磷化产物的结构。我们表明,不对称二膦可用作合成重要有机分子类别的磷类似物的构件。所描述的转化为合成带有磷酰基、磷酰基或硫代磷酰基官能团的有机磷化合物提供了一种新的方法。而且,
Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl, and amino substituents
and X-ray diffraction. The isolated unsymmetrical diphosphanes have no tendency to rearrange to the corresponding symmetrical species. Additionally, we proposed the general classification of diphosphanes based on the number of different groups attached to phosphorus atoms and their distribution within a molecule. To investigate the impact of substituents on the properties of P-centers and a molecule as
我们对具有不同取代基的二膦烷的合成,结构和性质进行了全面的研究。为此,我们合成了一系列新颖的通式为R 1 R 2 P-PR 3 R 4的烷基,芳基和氨基取代的二膦(其中R 1,R 2,R 3,R 4 = t Bu ,Ph,Et 2 N或iPr 2 N)通过卤代膦与金属磷化物的盐复分解反应,收率很高。通过获得第一个被单氨基和三氨基取代的系统,我们极大地扩展了这类化合物的范围。分离的化合物的结构通过NMR光谱和X射线衍射表征。分离出的不对称二膦烷没有重新排列为相应对称物质的趋势。此外,我们根据与磷原子连接的不同基团的数量及其在分子中的分布,提出了二膦的一般分类。为了研究取代基对P中心和整个分子的性质的影响,我们对获得的系统的电子和空间性质进行了DFT研究。
Zero-Valent Amino-Olefin Cobalt Complexes as Catalysts for Oxygen Atom Transfer Reactions from Nitrous Oxide
作者:Thomas L. Gianetti、Rafael E. Rodríguez-Lugo、Jeffrey R. Harmer、Monica Trincado、Matthias Vogt、Gustavo Santiso-Quinones、Hansjörg Grützmacher
DOI:10.1002/anie.201609173
日期:2016.12.5
several zero‐valent cobalt complexes with a bis(olefin)‐amino ligand is presented. Some of these complexes proved to be efficient catalysts for the selective oxidation of secondary and allylic phosphanes, as well as diphosphanes, even with a direct P−P bond. With 5 mol % catalyst loadings the oxidations proceed under mild conditions (25–70 °C, 7–22 h, 2 bar N2O) and afford good to excellent yields
介绍了几种具有双(烯烃)-氨基配体的零价钴配合物的合成和表征。这些络合物中的某些被证明是即使具有直接的P-P键也能选择性氧化仲和烯丙基膦以及二膦的有效催化剂。催化剂负载量为5 mol%时,氧化会在温和的条件下(25–70°C,7–22 h,2 bar N 2 O)进行,并提供良好至极好的收率(65–98%)。在此过程中,温室气体N 2 O被催化转化为良性N 2和增值有机磷化合物,其中一些很难以其他方式获得。