Mechanistic investigation of cis and trans oxidative addition to acetylacetonato-1,5-cyclooctadieneiridium(I)

Polyhedron ◽  
2017 ◽  
Vol 123 ◽  
pp. 252-258
Author(s):  
Jeanet Conradie
Keyword(s):  
Oxidative Addition ◽  
Mechanistic Investigation ◽  
Cis And Trans

Semisynthesis of cis- and trans-Solamin by Acidic Opening of Natural Diepomuricanin A − a Mechanistic Investigation

2001 ◽  
Vol 2001 (16) ◽  
pp. 3161 ◽  
Author(s):  
Christophe Gleye ◽  
Xavier Franck ◽  
Reynald Hocquemiller ◽  
Alain Laurens ◽  
Olivier Laprévote ◽  
...  
Keyword(s):  
Mechanistic Investigation ◽  
Cis And Trans

Dimethylplatinum(IV) Complexes With Cyanide: Thermal and Photoassisted Substitution Reactions, and Characterization of Products by N.M.R.

1987 ◽  
Vol 40 (9) ◽  
pp. 1565 ◽  
Author(s):  
TG Appleton ◽  
JR Hall ◽  
MA Williams
Keyword(s):  
Ultraviolet Irradiation ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Methyl Groups ◽  
Substitution Reactions ◽  
Aqueous Acid ◽  
Cyanide Ligands ◽  
Cis And Trans ◽  
Insoluble Precipitate

Reactions of cyanide with the dimethylplatinum (IV) complexes, [PtMe2(OH) (H20)1.5 n, [PtMe2Br2]n and fac-PtMe2Br(H2O)3+, have been studied, principally by 1H, 13C and 195Pt n.m.r. Cyanide rapidly displaces the ligands trans to the methyl groups. Subsequent reactions cis to the methyl groups occur more slowly with heating, or, for bromo complexes, on ultraviolet irradiation. These substitution reactions compete with reductive elimination of groups from the platinum(IV) compounds to produce platinum(II) products. All attempts to prepare solutions of fac-PtMe2(CN)(H2O)3+ were unsuccessful. Oxidative addition of ICN to cis-PtMe2( py )2 ( py = pyridine) gave PtMe2I(CN)( py )2, from which a solution of fac-PtMe2(CN)( MeOH )3+ in methanol could be obtained. Addition of water or aqueous acid to this solution gave a very insoluble precipitate of [PtMe2(CN)(OH)n. The cis and trans influences on Jpt -C and δC of the cyanide ligands have been evaluated.

Oxidative Addition of Haloalkanes to Metal Centers: A Mechanistic Investigation

2014 ◽  
Vol 33 (13) ◽  
pp. 3591-3595 ◽  
Author(s):  
Veeranna Yempally ◽  
Salvador Moncho ◽  
Sohail Muhammad ◽  
Edward N. Brothers ◽  
Bruce A. Arndtsen ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Metal Centers ◽  
Mechanistic Investigation

Oxidation of dimethylplatinum(II) complexes with malonyl peroxide derivatives

2015 ◽  
Vol 93 (1) ◽  
pp. 74-81 ◽  
Author(s):  
Richard J. Hazlehurst ◽  
Kyle R. Pellarin ◽  
Matthew S. McCready ◽  
Richard J. Puddephatt
Keyword(s):  
Phthalic Acid ◽  
Oxidative Addition ◽  
Membered Ring ◽  
Trans Isomers ◽  
Donor Ligand ◽  
Nitrogen Donor Ligand ◽  
Nitrogen Donor ◽  
Dicarboxylate Ligand ◽  
Cis And Trans

The reaction of the cyclic peroxides cyclobutane malonoyl peroxide and cyclopentane malonoyl peroxide to dimethylplatinum(II) complexes with the bidentate nitrogen donor ligand 4,4′-di-t-butyl-2,2′-bipyridine (bubpy) gave a mixture of the products of cis and trans oxidative addition, [PtMe2{(O2C)2C(C3H6)}(bubpy)] and [PtMe2{(O2C)2C(C4H8)}(bubpy)], respectively. The cis isomers exist with a chelating dicarboxylate ligand, forming a six-membered ring, while the trans isomers are thought to exist as oligomers, which may react with water or solvent to give complexes containing a monodentate dicarboxylate ligand. Equilibration of the product of cis oxidative addition, cis-[PtMe2{(O2C)2C(C3H6)}(bubpy)], with oxalic or phthalic acid to give equilibria with the oxalate cis-[PtMe2(O4C2)(bubpy)] or phthalate cis-[PtMe2{(O2C)2C6H4}(bubpy)] derivative, respectively, indicated the expected sequence of chelate stability oxalate > cyclobutane malonate > phthalate.

scholarly journals DABN Borazabicycles: Formation from MIDA Boronates and Synthetic Utility

2020 ◽  
Author(s):  
Sherif James Kaldas ◽  
chieh-hung tien ◽  
Gabriel dos Passos Gomes ◽  
Stephanie Meyer ◽  
martynas sirvinskas ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Transition State ◽  
Oxidative Addition ◽  
Mechanistic Investigation ◽  
Synthetic Utility

<div> <div> <div> <p>We report that coordinative hemilability allows the MIDA amine to behave as a nucleophile to intercept π-allyl intermediates. A mechanistic investigation indicates that this rearrangement proceeds through an SN2-like displacement at tetrasubstituted boron to furnish novel DABN (2,8- dioxa-5-aza-1-borabicyclo[3.3.1]nonane-3,7-dione) boronates. Oxidative addition into the N-C bond of the DABN scaffold reverses the reaction and furnishes borylated π-allyl intermediates that can then be trapped with complete linear selectivity. DFT calculations indicate that stabilizing interactions in the transition state, as well as the steric bulk of the MIDA unit, are the origins of the excellent regioselectivity. We further demonstrate the utility of our new reagents by way of a 3-component coupling that features allylammonium DABN boronates as linchpin reagents. This report disseminates a previously unknown aspect of MIDA boronates that can now be exploited. </p> </div> </div> </div>

Sign in / Sign up

Export Citation Format

Share Document