Quantifying Steric Effects of α-Diimine Ligands. Oxidative Addition of MeI to Rhodium(I) and Migratory Insertion in Rhodium(III) Complexes

2003 ◽  
Vol 22 (5) ◽  
pp. 1047-1054 ◽  
Author(s):  
Luca Gonsalvi ◽  
Joseph A. Gaunt ◽  
Harry Adams ◽  
Aurora Castro ◽  
Glenn J. Sunley ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Steric Effects ◽  
Diimine Ligands ◽  
Migratory Insertion

scholarly journals Chimera Diimine Ligands in Emissive [Cu(P^P)(N^N)][PF6] Complexes

Inorganics ◽  
2020 ◽  
Vol 8 (5) ◽  
pp. 33 ◽  
Author(s):  
Marco Meyer ◽  
Fabian Brunner ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Photophysical Properties ◽  
Phenyl Ether ◽  
Steric Effects ◽  
Single Crystal Structures ◽  
Diimine Ligands ◽  
Chelating Ligand ◽  
Tetrahedral Environment ◽  
Related Compounds

The syntheses and characterizations of the chelating ligand 6-chloro-6′-methyl-2,2′-bipyridine (6-Cl-6′-Mebpy) and of the copper(I) compounds [Cu(POP)(6-Cl-6′-Mebpy)][PF6] and [Cu(xantphos)(6-Cl-6′-Mebpy)][PF6] (POP = bis(2-(diphenylphosphanyl)phenyl)ether and xantphos = 4,5-bis(diphenylphosphanyl)-9,9-dimethyl-9H-xanthene) are described. The single crystal structures of both complexes were determined; the copper(I) ion is in a distorted tetrahedral environment and in [Cu(xantphos)(6-Cl-6′-Mebpy)][PF6], the disorder of the 6-Cl-6′-Mebpy ligand indicates there is no preference of the ‘bowl’-like cavity of the xanthene unit to host either the methyl or chloro-substituent, consistent with comparable steric effects of the two groups. The electrochemical and photophysical properties of [Cu(POP)(6-Cl-6′-Mebpy)][PF6] and [Cu(xantphos)(6-Cl-6′-Mebpy)][PF6] were investigated and are compared with those of the related compounds containing 6,6′-dichloro-2,2′-bipyridine or 6,6′-dimethyl-2,2′-bipyridine ligands. Trends in properties of the [Cu(P^P)(N^N)]+ complexes were consistent with 6-Cl-6′-Mebpy behaving as a combination of the two parent ligands.

Oxidative Addition of Methyl Iodide and CO Migratory Insertion in a Cationic Rhodium Complex of a S,N,S Tridentate Ligand

2003 ◽  
Vol 22 (12) ◽  
pp. 2535-2538 ◽  
Author(s):  
Mauro Bassetti ◽  
Alberto Capone ◽  
Lucilla Mastrofrancesco ◽  
Michela Salamone
Keyword(s):  
Methyl Iodide ◽  
Oxidative Addition ◽  
Rhodium Complex ◽  
Tridentate Ligand ◽  
Migratory Insertion

Kinetic-Mechanistic and Solid-State Study of the Oxidative Addition and Migratory Insertion of Iodomethane to [Rhodium(S,O-BdiPTorN,O-ox)(CO)(PR1R2R3)] Complexes

2018 ◽  
Vol 2018 (32) ◽  
pp. 3615-3625 ◽  
Author(s):  
Stefan Warsink ◽  
P. D. Riekert Kotze ◽  
J. M. Inus Janse van Rensburg ◽  
Johan A. Venter ◽  
Stefanus Otto ◽  
...  
Keyword(s):  
Solid State ◽  
Oxidative Addition ◽  
State Study ◽  
Migratory Insertion

Oxidative addition of monosilanes to planar iridium(I) complexes and carbonylation of the resulting adducts

1977 ◽  
Vol 30 (6) ◽  
pp. 1201 ◽  
Author(s):  
MA Bennett ◽  
R Charles ◽  
PJ Fraser
Keyword(s):  
Carbon Monoxide ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Steric Effects ◽  
Ambient Conditions ◽  
Tetragonal Pyramidal ◽  
Group 5 ◽  
Electronic And Steric Effects

Silanes [R3SiH; R3 = Cl3, MeCl2, (EtO)3, Ph3] undergo irreversible oxidative addition to planar iridium(I) complexes IrClL3 (L = PPh3, PMePh2 or AsPh3) to give silyliridium(III) hydrides IrHCl(SiR3)Ln (n = 2 or 3). The yellow, five-coordinate, probably tetragonal pyramidal complexes(n = 2) are formed mainly when L = PPh3 or AsPh3, and also in the case of L = PmePh2, R = Ph, whereas the colourless, six-coordinate, presumably octahedral adducts are formed predominantly when L = PMePh2. Both five- and six-coordinate adducts can be isolated from the addition of dichloro(methyl)silane to IrCl(AsPh3)3. Most of the adducts react with carbon monoxide under ambient conditions to give silyliridium(III) hydrido carbonyls, IrHCl(SiR3)(CO)L2, which may undergo partial or complete reductive elimination to IrCl(CO)L2 and R3SiH; the ease with which this occurs depends on L (PPh3 > PMePh2 > AsPh3) and on R3 [Ph3 > (EtO)3 > Cl3 ≈ MeCl2]. The reactions of silanes with IrClL3, RhClL3 and IrCl(CO)(PPh3)2 are compared, and the trends observed in the case of IrClL3 are discussed in terms of electronic and steric effects in the silyl and Group 5 donors. Structural assignments for the new complexes are based on i.r., far-i.r. and 1H N.M.R. data.

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