POCOP-Type Pincer Complexes of Nickel: Synthesis, Characterization, and Ligand Exchange Reactivities of New Cationic Acetonitrile Adducts

2015 ◽  
Vol 34 (14) ◽  
pp. 3520-3531 ◽  
Author(s):  
Sébastien Lapointe ◽  
Boris Vabre ◽  
Davit Zargarian
2021 ◽  
Author(s):  
Naser Rahimi ◽  
Davit Zargarian

Stirring acetonitrile solutions of the charge-neutral pincer complexes (POCN)NiBr (1, POCN= ΚP,ΚC,ΚN-{2-(i-Pr)2PO,6-CH2{c-N(CH2)5}-C6H3) and (POCOP)NiBr (2, POCOP= ΚP,ΚC,ΚP'-2,6-(i-Pr2PO)2}C6H3) with AgSbF6 facilitates Br- abstraction to give the corresponding cationic acetonitrile adducts [(POCN)Ni(NCMe)]+,...


2008 ◽  
Vol 20 (4) ◽  
pp. 585-594 ◽  
Author(s):  
J. Ma ◽  
J. Cao ◽  
M. J. Ding ◽  
L. H. Yuan ◽  
M. J. Zhai ◽  
...  

2020 ◽  
Author(s):  
Matthew Stout ◽  
Brian Skelton ◽  
Alexandre N. Sobolev ◽  
Paolo Raiteri ◽  
Massimiliano Massi ◽  
...  

<p>Three Re(I) tricarbonyl complexes, with general formulation Re(N^L)(CO)<sub>3</sub>X (where N^L is a bidentate ligand containing a pyridine functionalized in the position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo) were synthesized and their reactivity explored in terms of solvent-dependent ligand substitution, both in the ground and excited states. When dissolved in acetonitrile, the complexes bound to the thione ligand underwent ligand exchange with the solvent resulting in the formation of Re(NCMe)<sub>2</sub>(CO)<sub>3</sub>X. The exchange was found to be reversible, and the starting complex was reformed upon removal of the solvent. On the other hand, the complexes appeared inert in dichloromethane or acetone. Conversely, the complex bound to the thiazole-2-ylidene ligand did not display any ligand exchange reaction in the dark, but underwent photoactivated ligand substitution when excited to its lowest metal-to-ligand charge transfer manifold. Photolysis of this complex in acetonitrile generated multiple products, including Re(I) tricarbonyl and dicarbonyl solvato-complexes as well as free thiazole-2-ylidene ligand.</p>


2018 ◽  
Author(s):  
Tasneem Siddiquee ◽  
Abdul Goni

Chemical treatment of CoX<sub>2</sub><b><sup>. </sup></b>6H<sub>2</sub>O (X = Cl, Br, I) with the potentially tridentate PNP pincer ligand 2,6-bis(di-<i>tert</i>-butylphosphinomethyl)pyridine in 1:1 molar ratio results in cobalt(II) halide-PNP pincer complexes. The effect of the hydrated metal source on molecular structure and geometry of the complexes was studied by single crystal X-ray diffraction analysis. The complexes are neutral and the cobalt center adopts a penta-coordinate system with potential atropisomerization. Within the unit cell there are two distinct molecules per asymmetric unit. One of the two phosphorus atoms in the PNP ligand was observed to be partially oxidized to phosphinoxide. Disorder in the structure reflects a mixture of square pyramidal and distorted tetrahedral geometry.


1995 ◽  
Vol 60 (7) ◽  
pp. 1140-1157 ◽  
Author(s):  
Ljiljana S. Jovanovic ◽  
Luka J. Bjelica

The electrochemistry of four novel Fe(III) complexes of the type [Fe(L)Cl], involving quadridentate ligands based on the condensation products of benzoylacetone-S-methylisothiosemicarbazone with salicylaldehyde, 5-chlorosalicylaldehyde, 3,5-dichlorosalicylaldehyde or 5-nitrosalicylaldehyde, was studied in DMF and DMSO at a GC electrode. All complexes undergo a two-step one-electron reductions, usually complicated by chemical reactions. In solutions containing Cl-, the ligand-exchange reactions Cl--DMF and Cl--DMSO take place. Stability of the chloride-containing complexes was discussed in terms of the coordinated ligand effect, oxidation state of the central atom and, in particular, of the donor effect of the solvent. Some relevant kinetic data were calculated.


2019 ◽  
Vol 2 (10) ◽  
pp. 6135-6143 ◽  
Author(s):  
Haodong Tang ◽  
Jialin Zhong ◽  
Wei Chen ◽  
Kanming Shi ◽  
Guanding Mei ◽  
...  

1998 ◽  
Vol 53 (11) ◽  
pp. 1267-1272 ◽  
Author(s):  
Jörg J. Schneider ◽  
Dirk Wolf

The arene ligand exchange mechanism of slipped arene triple deckers [Bis{(η5-CpR)Co}-μ-{η4:η4-arene}] (R = Me5, 1,2,4 tri-tert butyl, arene = benzene, toluene) 1 was studied by 1H-NMR spectroscopy for different concentrations and solvents. It has been found that triple deckers of type 1 decompose slowly in solution. A unique equilibrium, between these triple deckers and the mixed sandwich complexes [(η6-arene)Co(η5-CpR)] and 14 e [(η5-Cp)Co]solv fragments generated in situ by decomposition o f 1 exists. In addition to this equilibrium arene lability of the thus formed mixed sandwich complex type has been detected by NMR making slipped triple deckers 1 ideal single source compounds for the generation of two [(η5-Cp)Co] fragments in one reaction step. Such fragments are valuable metal ligand components with high synthetic utility in organometallic chemistry.


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