Energetics of Migratory Insertion Reactions in Pd(II) Acyl Ethylene, Alkyl Ethylene, and Alkyl Carbonyl Complexes

1995 ◽  
Vol 117 (3) ◽  
pp. 1137-1138 ◽  
Author(s):  
Francis C. Rix ◽  
Maurice Brookhart
Keyword(s):  
Carbonyl Complexes ◽  
Insertion Reactions ◽  
Migratory Insertion

CO and Ethylene Migratory Insertion Reactions and Copolymerization Involving Palladium Complexes of a NiN2S2Metallodithiolate Ligand

2007 ◽  
Vol 26 (4) ◽  
pp. 783-792 ◽  
Author(s):  
Marilyn V. Rampersad ◽  
Erik Zuidema ◽  
Jan Meine Ernsting ◽  
Piet W. N. M. van Leeuwen ◽  
Marcetta Y. Darensbourg
Keyword(s):  
Palladium Complexes ◽  
Insertion Reactions ◽  
Migratory Insertion

PX3-induced migratory insertion reactions of half-sandwich-type carbenerhodium(I) complexes

2001 ◽  
Vol 25 (3) ◽  
pp. 396-399 ◽  
Author(s):  
Ulrich Herber ◽  
Rita Guerrero Sanchez ◽  
Olaf Gevert ◽  
Matthias Laubender ◽  
Helmut Werner
Keyword(s):  
Insertion Reactions ◽  
Migratory Insertion ◽  
Sandwich Type ◽  
Half Sandwich

scholarly journals 1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 686
Author(s):  
Małgorzata Walewska ◽  
Judith Baumgartner ◽  
Christoph Marschner
Keyword(s):  
Insertion Reactions ◽  
Insertion Product ◽  
Migratory Insertion ◽  
Chloride Elimination ◽  
Related Reaction

The reactions of the PMe3 adduct of the silylated germylene [(Me3Si)3Si]2Ge: with GeCl2·dioxane were found to yield 1,1-migratory insertion products of GeCl2 into one or two Ge–Si bonds. In a related reaction, a germylene was inserted with tris(trimethylsilyl)silyl and vinyl substituents into a Ge–Cl bond of GeCl2. This was followed by intramolecular trimethylsilyl chloride elimination to another cyclic germylene PMe3 adduct. The reaction of the GeCl2 mono-insertion product (Me3Si)3SiGe:GeCl2Si(SiMe3)3 with Me3SiC≡CH gave a mixture of alkyne mono- and diinsertion products. While the reaction of a divinylgermylene with GeCl2·dioxane only results in the exchange of the dioxane of GeCl2 against the divinylgermylene as base, the reaction of [(Me3Si)3Si]2Ge: with one GeCl2·dioxane and three phenylacetylenes gives a trivinylated germane with a chlorogermylene attached to one of the vinyl units.

A DFT STUDY OF CO MIGRATORY INSERTION REACTIONS WITH A NEW TYPE OF GROUP 10 METAL-ALKYL AND METAL-ALKOXIDE BONDS

2012 ◽  
Vol 11 (01) ◽  
pp. 1-17 ◽  
Author(s):  
SIWEI BI ◽  
JUNFENG ZHAO ◽  
WEI FAN ◽  
PING LI
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Metal Alkoxide ◽  
Insertion Reactions ◽  
Functional Theory ◽  
Step Process ◽  
Migratory Insertion ◽  
One Step ◽  
New Type

The CO migratory insertion into M–O and M–C bonds of the new model (PMe3)2M(η2 – CH2CH2O) ( M = Ni , Pd and Pt ) (model (d)) proposed in this work has been studied with the aid of density functional theory (DFT) calculations. It is found (1) when M = Ni , CO migratory insertion into Ni–C is thermodynamically and kinetically favored, and (2) when M = Pd and Pt , the insertion into M–O bond via a one-step process is preferred. Further investigation on CO migratory insertion using Pt(PMe3)2(C7H10O) (R′-Pt) derived from the experimental compound Pt(PEt3)2(C7H10O) gives the same conclusions as model (d) with M = Pt . Results obtained from the reaction of model (d) ( M = Pt ) with CO are consistent with the experimental observation that CO prefers to insert into Pt–O bond of Pt(PEt3)2(C7H10O) .

scholarly journals Unexpected Migratory Insertion Reactions of M(alkyl)2 (M=Zn, Cd) and Diamidocarbenes

2015 ◽  
Vol 21 (8) ◽  
pp. 3215-3218 ◽  
Author(s):  
Lee R. Collins ◽  
Gabriele Hierlmeier ◽  
Mary F. Mahon ◽  
Ian M. Riddlestone ◽  
Michael K. Whittlesey
Keyword(s):  
Insertion Reactions ◽  
Migratory Insertion

An Unprecedented Type of Migratory Insertion Reactions of Unsaturated C3 Units into Rh−O and Rh−C Bonds

2001 ◽  
Vol 7 (9) ◽  
pp. 1959-1967 ◽  
Author(s):  
Helmut Werner ◽  
Ralf Wiedemann ◽  
Matthias Laubender ◽  
Bettina Windmüller ◽  
Justin Wolf
Keyword(s):  
Insertion Reactions ◽  
Migratory Insertion

Hydrido(acylenolato)cobalt(III)-Verbindungen mit Trimethylphosphan- Liganden: Insertionsreaktionen mit Alkinen und die ersten Carbonylcobalt(III)-Komplexe / Hydrido(acylenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands: Insertion Reactions with Alkynes and the First Carbonylcobalt(III) Complexes

2000 ◽  
Vol 55 (8) ◽  
pp. 707-717 ◽  
Author(s):  
Hans-Friedrich Klein ◽  
Xiaoyan Li ◽  
Ulrich Flörke ◽  
Hans-Jürgen Haupt
Keyword(s):  
Axial Position ◽  
Coupling Reactions ◽  
Carbonyl Complexes ◽  
Ambient Conditions ◽  
X Ray Diffraction ◽  
Insertion Reactions ◽  
X Ray ◽  
Reversible Transformation ◽  
Tert Butyl ◽  
Trigonal Bipyramidal

Abstract Formal insertion of phenylethyne into Co-H functions of mer-octahedral acyl(enolato)-cobalt(III) hydrides 1-3 proceeds under ambient conditions affording η1-vinylcobalt(III) compounds where the dianionic acyl(enolato) ligands are derived from 2-formyl-4-phenyl-cyclohexanone (4), 1-formyl-cyclohexan-2-one (5), and 3-hydroxo-2,3-diphenyl-propenal (6). Dissociation and association of trimethylphosphane results in a reversible transformation of penta-coordinate complexes 4 -6 into hexa-coordinate ones 7 -9, respectively, involving different tautomeric vinyl species. In toluene solution 9 rearranges by reductive C,C coupling into a 5,6-η2-olefin(enolato)cobalt(I) complex 10. Trimethylsilylethyne undergoes a hydrolytic desilylation reaction which is followed by reductive C,C-coupling reactions of acyl and vinyl functions selectively producing chelating η1-enolato-5,6-η2-olefin ligands in cobalt(I) com ­ pounds 13 -16 where the (ax,eq)chelating ligands are derived from 1-formyl-cyclohexan-2-one (13), 3-hydroxo-2,3-diphenyl-propenal (14), 2-formyl-α-tetralone (15), and 2-formyl-4-tert-butyl-cyclohexanone (16). An axial position of the enolato-O donor in the trigonal bipyramidal configuration of complex 15 has been confirmed by X-ray diffraction analysis. With 1,4-bis(trimethylsilyl)buta-diyne 1,2-addition in cobalt(III) hydrides 2, 3, 11 (as deriverd from 2-formyl-α-tetralone), and 12 (as derived from 2-formyl-4-tert-butyl-cyclohexanone) produces 2-metalated vinyl groups in compounds 17 -20. Dissociation of trimethylphosphane from 17 and 19 does not activate C,C coupling at the cobalt(III) centre of penta-coordinate 21 and 22. Steric congestion in compounds 17, 18, and 20 favours exchange of trimethylphosphine for carbon monoxide affording the first octahedral carbonyl complexes of cobalt (d6) (23 -25). In the crystal and in solution a meridional configuration is adopted by complex 23 with the CO group in a position opposite to the acyl function.

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