已制备并表征了二聚杂配l酰胺配合物[(2,6-(3,5-Me 2 C 6 H 3)2 C 6 H 3 NH)Yb(N(SiMe 3)2)] 2(1)并对其进行了表征。这种二价三联苯胺基络合物能够以极低的催化剂负载量对各种末端烯烃进行高度区域选择性的氢化硅烷化。的反应1与苯基硅烷在高温下导致硅烷与一terphenylamide配体和配体酰胺再分配脱氢耦合经由一个高价硅烷中间体,其已经光谱表征。
Cobalt-Catalyzed Regiodivergent Hydrosilylation of Vinylarenes and Aliphatic Alkenes: Ligand- and Silane-Dependent Regioselectivities
作者:Chao Wang、Wei Jie Teo、Shaozhong Ge
DOI:10.1021/acscatal.6b02518
日期:2017.1.6
hydrosilylation of alkenes catalyzed by catalysts generated in situ from bench-stable Co(acac)2 and phosphine- or nitrogen-based ligands. A wide range of vinylarenes and aliphatic alkenes reacted to afford either branched (45 examples) or linear (37 examples) organosilanes in high isolated yields (average: 84%) and high regioselectivities (from 91:9 to >99:1). This transformation tolerates a variety of functional
Unexpected catalytic activity of simple triethylborohydrides in the hydrosilylation of alkenes
作者:M. Zaranek、S. Witomska、V. Patroniak、P. Pawluć
DOI:10.1039/c7cc01531c
日期:——
triethylborohydride-catalysed hydrosilylation of alkenes is reported. The hydrosilylation of certain alkenes, in particular styrenes, vinylsilanes and allyl glycidyl ether, with aromatic hydrosilanes proceeded in a highlyregioselective manner to give Markovnikov products. It is significant that several protocols use NaHBEt3 as a reducing agent generating active catalysts in situ of other hydrosilylation reactions. An
Cyclic (Alkyl)(amino)carbene Lanthanide Amides: Synthesis, Structure, and Catalytic Selective Hydrosilylation of Alkenes
作者:Zexiong Pan、Jianying Zhang、Lulu Guo、Hao Yang、Jianfeng Li、Chunming Cui
DOI:10.1021/acs.inorgchem.1c01780
日期:2021.9.6
The first examples of cyclic (alkyl)(amino)carbene (CAAC) lanthanide (Ln) complexes were synthesized from the reaction of CAAC with Yb[N(SiMe3)2]2 and Eu[N(SiMe3)2]2(THF)2 (THF = tetrahydrofuran). The structures of (CAAC)Yb[N(SiMe3)2]2 (2) and (CAAC)Eu[N(SiMe3)2]2(THF) (3) were determined by X-ray diffraction analysis. Density functional theory calculations of 2 revealed the predominantly ionic bond
communication, we synthesized and characterized a series of new cobalt(II) chloride bench-stable precatalysts coordinated to a small library of structurally similar Schiff base ligands. Thus the synthesized species were evaluated for their ability to act as olefin hydrosilylation catalysts in the presence of alkali metal triethylborohydrides. From the crystal engineering point of view, it was observed that
环境和经济方面使得寻找新的非贵金属氢化硅烷化催化剂成为最新挑战。钴是基准铂族物种的有趣替代品,尽管如此,钴的相对婴儿期仍需要进一步研究,特别是关于装饰催化活性金属中心的有机配体的结构。作为我们先前交流的延续,我们合成并表征了一系列与结构相似的席夫碱配体的小型文库配合使用的新型氯化钴(II)台式稳定的预催化剂。因此,评价了合成物质在碱金属三乙基硼氢化物存在下充当烯烃氢化硅烷化催化剂的能力。从晶体工程学的角度来看,L Cl 2 ]“开放”或[Co L 2 ] 2+ “封闭”物质或它们的混合物。这影响了它们的催化性能,就氢化硅烷化选择性和最低的催化剂载量而言,苯并咪唑/ 2H-咪唑“开放”体系是最有效的。总而言之,我们的工作表明,看似相似的配位基序不一定会导致催化开放的钴(II)配位化合物的同构基团,这是一般设计新催化剂时要考虑的重要因素。
Synthesis of divalent ytterbium terphenylamide and catalytic application for regioselective hydrosilylation of alkenes
作者:Yinghua Shi、Jianfeng Li、Chunming Cui
DOI:10.1039/c7dt01837a
日期:——
5-Me2C6H3)2C6H3NH)Yb(N(SiMe3)2)]2 (1) has been prepared and characterized. This divalent terphenylamido complex enabled highly regioselective hydrosilylation of various terminal alkenes with very low catalyst loadings. The reaction of 1 with phenylsilane at high temperature led to the dehydrogenative coupling of silane with a terphenylamide ligand and redistributions of amide ligands via a hypervalent
已制备并表征了二聚杂配l酰胺配合物[(2,6-(3,5-Me 2 C 6 H 3)2 C 6 H 3 NH)Yb(N(SiMe 3)2)] 2(1)并对其进行了表征。这种二价三联苯胺基络合物能够以极低的催化剂负载量对各种末端烯烃进行高度区域选择性的氢化硅烷化。的反应1与苯基硅烷在高温下导致硅烷与一terphenylamide配体和配体酰胺再分配脱氢耦合经由一个高价硅烷中间体,其已经光谱表征。