Formation of PCP pincer cobalt complexes with cobaltacyclopropane moieties via double Csp3–H bond activation

RSC Advances ◽  
2015 ◽  
Vol 5 (25) ◽  
pp. 19402-19408 ◽  
Author(s):  
Gengyu Zhu ◽  
Lin Wang ◽  
Hongjian Sun ◽  
Xiaoyan Li
Keyword(s):  
Carbon Atom ◽  
Bond Activation ◽  
Cobalt Complexes ◽  
Pcp Pincer

The introduction and changes of the substituents at the middle carbon atom of the preligand dipyrrolmethane have a significant impact on the reaction results.

Phosphine-assisted C–H bond activation in Schiff bases and formation of novel organo cobalt complexes bearing Schiff base ligands

2018 ◽  
Vol 42 (6) ◽  
pp. 4646-4652 ◽  
Author(s):  
Hua Zhang ◽  
Junyang Xing ◽  
Yanhong Dong ◽  
Shangqing Xie ◽  
Shishuai Ren ◽  
...  
Keyword(s):  
Schiff Base ◽  
Schiff Bases ◽  
Bond Activation ◽  
Cobalt Complexes ◽  
Schiff Base Ligands

The sp2 C–H bond activation of the HCN moiety in diphenylphosphino benzalimines was realized using CoMe(PMe3)4 with the elimination of methane.

Preparation of hydrido [CNC]-pincer cobalt complexes via selective C–H/C–F bond activation and their catalytic performances

2018 ◽  
Vol 42 (19) ◽  
pp. 15578-15586 ◽  
Author(s):  
Fei Yang ◽  
Yangyang Wang ◽  
Faguan Lu ◽  
Shangqing Xie ◽  
Xinghao Qi ◽  
...  
Keyword(s):  
Carbonyl Compounds ◽  
Bond Activation ◽  
Cobalt Complexes ◽  
Catalytic Performances

[CNC]-pincer Co hydrides were synthesized via selective C–H/C–F activation and catalyzed hydrosilylation of carbonyl compounds.

Selective C−C vs C−H Bond Activation by Rhodium(I) PCP Pincer Complexes. A Computational Study

2000 ◽  
Vol 122 (29) ◽  
pp. 7095-7104 ◽  
Author(s):  
Andreas Sundermann ◽  
Olivier Uzan ◽  
David Milstein ◽  
Jan M. L. Martin
Keyword(s):  
Bond Activation ◽  
Computational Study ◽  
Pincer Complexes ◽  
Pcp Pincer

scholarly journals Imido Cobalt Complexes with Imidyl Character

2021 ◽  
Author(s):  
alexander Reckziegel ◽  
Manjinder Kour ◽  
Beatrice Battistella ◽  
Stefan Mebs ◽  
Katrin Beuthert ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Spin Density ◽  
High Spin ◽  
Bond Activation ◽  
High Spin State ◽  
Cobalt Complexes ◽  
Spectroscopic Methods ◽  
Computational Studies ◽  
Ancillary Ligand ◽  
Unpaired Spin

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L<sub>2</sub>)<sup>–</sup>, (L = N(Dipp)SiMe<sub>3</sub>), Dipp = 2,6-diisopropylphenyl) bearing very long Co–NAryl bonds of around 1.75 Å. The electronic structure was interrogated using a variety of physical and spectroscopic methods indicating the first authenticated examples of cobalt bound imidyl species. Computational studies corroborate these findings and reveal that the high-spin state of these complexes gives rise to unpaired spin-density on the imide nitrogen and leads to its imidyl character. Obtained complexes are capable of intermolecular H atom abstraction from C–H bonds that yields the corresponding cobalt amides. Exchange of the Dipp-substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me<sub>3</sub>Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.<br>

scholarly journals Crystal structure of an iridium(III) complex of the [C(dppm)2] PCP pincer ligand system and its conjugate CH acid form

2018 ◽  
Vol 74 (5) ◽  
pp. 620-624 ◽  
Author(s):  
Christian Reitsamer ◽  
Inge Schlapp-Hackl ◽  
Gabriel Partl ◽  
Walter Schuh ◽  
Holger Kopacka ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Iridium Complexes ◽  
Pincer Ligand ◽  
Single Crystal Diffraction ◽  
Dalton Trans ◽  
Ligand System ◽  
Distorted Octahedral ◽  
Major Interest ◽  
Carbonyl Bond ◽  
Pcp Pincer

After the successful creation of the newly designed PCP carbodiphosphorane (CDP) ligand [Reitsamer et al. (2012). Dalton Trans. 41, 3503–3514; Stallinger et al. (2007). Chem. Commun. pp. 510–512], the treatment of this PCP pincer system with the transition metal iridium and further the analysis of the structures by single-crystal diffraction and by NMR spectroscopy were of major interest. Two different iridium complexes, namely (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}methane-κ3 P,C,P′)carbonylchloridohydridoiridium(III) chloride dichloromethane trisolvate, [IrIII(CO){C(dppm)2-κ3 P,C,P′}ClH]Cl·3CH2Cl2 (1) and the closely related (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}methanide(1+)-κ3 P,C,P′)carbonylchloridohydridoiridium(III) dichloride–hydrochloric acid–water (1/2/5.5), [IrIII(CO){CH(dppm)2-κ3 P,C,P′)ClH]Cl}2 (2), have been designed and both complexes show a slightly distorted octahedral coordinated IrIII centre. The PCP pincer ligand system is arranged in a meridional manner, the CO ligand is located trans to the central PCP carbon and a hydride and chloride are located perpendicular above and below the P2C2 plane. With an Ir—CCDP distance of 2.157 (5) Å, an Ir—CO distance of 1.891 (6) Å and a quite short C—O distance of 1.117 (7) Å, complex 1 presents a strong carbonyl bond. Complex 2, the corresponding CH acid of 1, shows an additionally attached proton at the carbodiphosphorane carbon atom located antiperiplanar to the hydride of the metal centre. In comparison with complex 1, the Ir—CCDP distance of 2.207 (3) Å is lengthened and the Ir—C—O values indicate a weaker trans influence of the central carbodiphosphorane carbon atom.

scholarly journals Imido Cobalt Complexes with Imidyl Character

2021 ◽  
Author(s):  
alexander Reckziegel ◽  
Manjinder Kour ◽  
Beatrice Battistella ◽  
Stefan Mebs ◽  
Katrin Beuthert ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Spin Density ◽  
High Spin ◽  
Bond Activation ◽  
High Spin State ◽  
Cobalt Complexes ◽  
Spectroscopic Methods ◽  
Computational Studies ◽  
Ancillary Ligand ◽  
Unpaired Spin

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L<sub>2</sub>)<sup>–</sup>, (L = N(Dipp)SiMe<sub>3</sub>), Dipp = 2,6-diisopropylphenyl) bearing very long Co–NAryl bonds of around 1.75 Å. The electronic structure was interrogated using a variety of physical and spectroscopic methods indicating the first authenticated examples of cobalt bound imidyl species. Computational studies corroborate these findings and reveal that the high-spin state of these complexes gives rise to unpaired spin-density on the imide nitrogen and leads to its imidyl character. Obtained complexes are capable of intermolecular H atom abstraction from C–H bonds that yields the corresponding cobalt amides. Exchange of the Dipp-substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me<sub>3</sub>Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.<br>

Synthesis and reactivity of silyl cobalt complexes bearing a tetradentate phosphino silyl ligand via Si–H bond activation

Polyhedron ◽  
2018 ◽  
Vol 143 ◽  
pp. 165-170 ◽  
Author(s):  
Peng Zhang ◽  
Shilu Xu ◽  
Xiaoyan Li ◽  
Xinghao Qi ◽  
Hongjian Sun ◽  
...  
Keyword(s):  
Bond Activation ◽  
Cobalt Complexes
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