Electronic Effects on the β-Alkyl Migratory Insertion Reaction ofpara-Substituted Styrene Methyl Palladium Complexes

: Migratory insertion is a fundamental organometallic transformation that enables the functionalization of an unsaturated bond. Recent reports on catalytic hydroamination provide evidence that supports an intermolecular migratory insertion pathway featuring alkene insertion into metal-nitrogen (M-N) bonds. This article presents factors influencing the rate of migratory insertion in late-transition metal-catalyzed hydroamination, including steric and electronic effects from ligands, alkenes, and metal centers, along with stabilization from coordinated amine intermediates and ordered transition states.

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Allyl–palladium complexes with fluorinated benzene thiolate ligands. Examination of the electronic effects in the Pd-catalyzed allylic alkylation reaction with the catalytic system [(η3-C3H5)Pd(μ-SRf)]2/PR3

Journal of Organometallic Chemistry ◽

10.1016/s0022-328x(02)01225-1 ◽

2002 ◽

Vol 654 (1-2) ◽

pp. 16-20 ◽

Cited By ~ 14

Author(s):

Rocı́o Redón ◽

Hugo Torrens ◽

Zhaohui Wang ◽

David Morales-Morales

Keyword(s):

Catalytic System ◽

Palladium Complexes ◽

Alkylation Reaction ◽

Allylic Alkylation ◽

Electronic Effects ◽

Thiolate Ligands

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Highly Chemo-, Regio-, and Stereoselective Carbon−Carbon Bond Formation via Migratory Insertion Reaction of Zirconacyclopentene Derivatives and Alkynyl Metals Containing Li and Mg. Novel Synthesis of 1,5-Dienes and 1,5-Enynes

Journal of the American Chemical Society ◽

10.1021/ja990266+ ◽

1999 ◽

Vol 121 (48) ◽

pp. 11223-11224 ◽

Cited By ~ 26

Author(s):

Yves Dumond ◽

Ei-ichi Negishi

Keyword(s):

Bond Formation ◽

Insertion Reaction ◽

Carbon Bond ◽

Novel Synthesis ◽

Carbon Carbon Bond ◽

Migratory Insertion

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Migratory insertion reaction in alkenyl ruthenium(II) complexes containing a trifluoroacetate ligand. X-ray structure of the Ru(η2- O2CCF3)(η1-OCCHCHtBu)(CO)(PPh3)2 complex

Inorganic Chemistry Communications ◽

10.1016/s1387-7003(99)00095-7 ◽

1999 ◽

Vol 2 (8) ◽

pp. 364-367 ◽

Cited By ~ 6

Author(s):

Lluı̈sa Matas ◽

Josep Muniente ◽

Josep Ros ◽

Ángel Alvarez-Larena ◽

Joan F. Piniella

Keyword(s):

Insertion Reaction ◽

X Ray ◽

Migratory Insertion

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Syntheses and reactivity of square-planar Rh(I) complexes, LRh(CO) (L = unsymmetric tridentate chelating pyrazolylgallate ligand). X-ray crystal structures of [Me2Gapz(OCH2CH2NH2)]Rh(CO) and [Me2Gapz(OCH2CH2NMe2)]Rh(COMe)I (pz = pyrazolyl, N2C3H3)

Canadian Journal of Chemistry ◽

10.1139/v85-501 ◽

1985 ◽

Vol 63 (11) ◽

pp. 3019-3026 ◽

Cited By ~ 10

Author(s):

Brenda M. Louie ◽

Steven J. Rettig ◽

Alan Storr ◽

James Trotter

Keyword(s):

Crystal Structures ◽

Heavy Atom ◽

Least Square ◽

Insertion Reaction ◽

Space Group ◽

Physical Measurements ◽

Square Planar ◽

Migratory Insertion ◽

Complex Crystal

The syntheses and characterization of a number of square-planar Rh(I) monocarbonyl complexes incorporating un-symmetrical, tridentate, pyrazolylgallate ligands in a meridional coordination mode are described. Oxidative addition reactions of these complexes are detailed and a facile migratory insertion reaction, following the addition of methyl iodide, has resulted in a five-coordinate square-pyramidal Rh(III) acetyl complex. Crystal structures of two compounds are presented, [Me2Gapz(OCH2CH2NH2)]Rh(CO) and [Me2Gapz(OCH2CH2NMe2)]Rh(COMe)I, and confirm the molecular arrangements predicted on the basis of other physical measurements. Crystals of the former are monoclinic, a = 10.212(2), b = 7.8484(5), c = 16.733(2) Å, β = 105.133(6)°, z = 4, space group P21/c; and those of the latter are monoclinic, a = 10.0960(11), b = 11.5352(8), c = 15.871(2) Å, β = 105.764(6)°, z = 4, space group P21/n. Both structures were solved by conventional heavy atom methods and were refined by full-matrix least-square procedures to R = 0.026 and 0.036, respectively, for 2142 and 2941 reflections with I ≥ 3σ(I).

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