Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex
作者:Roberto Nolla‐Saltiel、Ana M. Geer、Laurence J. Taylor、Olivia Churchill、E. Stephen Davies、William Lewis、Alexander J. Blake、Deborah L. Kays
DOI:10.1002/adsc.202000514
日期:2020.8.4
Herein we report the synthesis of three heteroleptic first‐row transitionmetal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)‐carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt‐catalysed hydrophosphination process that solely and selectively
Bis(boryl)metallocenes. 2.<sup>1</sup> Syntheses of 1,1‘-Bis(boryl)cobaltocenium Complexes
作者:Gerhard E. Herberich、Ulli Englert、Andreas Fischer、Dag Wiebelhaus
DOI:10.1021/om980465m
日期:1998.10.1
h)Cl, (1b)AlCl4, and (1b)PF6; (ii) zwitterionic or semiquaternized compounds (type B) with one trigonal and one tetrahedralboron center such as 5, 9, and 10; of these, 5 is fluxional in solution with two effectively equivalent ligands while 9 and 10 display static structures; and (iii) the inverse chelate structure of 11 (type C) which is found in the crystal and in solution.
双(硼基)钴铝Co(C 5 H 4 BR 2)2(1)可由CoBr 2(DME)和碱金属硼基环戊二烯化物M(C 5 H 4 BR 2)(M = Li,Na)(2)制得。以这种方式可以获得两种二烷基氨基化合物1c(R = NMe 2)和1d(R = NEt 2)。用C 2 Cl 6氧化可提供离子型钴钴氯化物(1c)Cl和(1dCl。可以通过修饰硼上的取代基来合成其他钴ce化合物。用过量的BCl 3处理(1d)Cl得到高反应性的氯化物Co(C 5 H 4 BCl 2)(C 5 H 4 BCl 3)(5)。然后对5进行Pinacolysis,得到单取代产物Co [C 5 H 4 B(OCMe 2)2 ](C 5 H 4 BCl 3)(9)和分解产物[Co C 5 H 4B(OCMe 2)2 } 2 ] Cl [(1h)Cl]分别取决于化学计量和反应条件。5与四甲基锡的反应用甲基取代两个氯原子,得到Co(C
Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H<sub>2</sub>
pyridine to 1 or photolyzed solutions of [(ketguan)Co(N3)(py)]2 (4a) leads to destabilization via activation of the nitride unit, resulting in the mixed-valent Co(II)/(III) bridged imido species [(ketguan)Co(py)][(ketguan)Co](μ-NH)(μ-N¬3) (5) formed from intermolecular hydrogen atom abstraction (HAA) of strong C-H bonds (BDE ~ 100 kcal/mol). Kinetic rate analysis of the formation of 5 in the presence of C6H12