Oxidative Addition of HSnR3 (R = Ph, Bu) to the Square-Planar Iridium(I) Compounds Ir(XR)(TFB)(PCy3) (XR = OMe, OEt, OCHMe2, OPh, SPr) and Ir(C2Ph)L2(PCy3) (L2 = TFB, 2CO)

1995 ◽  
Vol 14 (7) ◽  
pp. 3486-3496 ◽  
Author(s):  
Miguel A. Esteruelas ◽  
Fernando J. Lahoz ◽  
Montserrat Olivan ◽  
Enrique Onate ◽  
Luis A. Oro
Keyword(s):  
Oxidative Addition ◽  
Square Planar

Acid-Catalyzed Oxidative Addition of a C–H Bond to a Square Planar d8 Iridium Complex

2014 ◽  
Vol 136 (25) ◽  
pp. 8891-8894 ◽  
Author(s):  
Jason D. Hackenberg ◽  
Sabuj Kundu ◽  
Thomas J. Emge ◽  
Karsten Krogh-Jespersen ◽  
Alan S. Goldman
Keyword(s):  
Oxidative Addition ◽  
Iridium Complex ◽  
Square Planar ◽  
Acid Catalyzed

Activation entropy as a dominant factor in the oxidative addition of some group IV hydrides to an iridium(I) complex

1976 ◽  
Vol 54 (19) ◽  
pp. 3102-3109 ◽  
Author(s):  
J. P. Fawcett ◽  
J. F. Harrod
Keyword(s):  
Relative Rate ◽  
Oxidative Addition ◽  
Group Iv ◽  
Dominant Factor ◽  
Iridium Complex ◽  
Activation Entropy ◽  
Acid Base ◽  
Square Planar ◽  
The Difference ◽  
Kinetics Of

The kinetics of the reactions[Formula: see text]have been studied (M = Si, Ge, Sn). All three reactions proceed by predissociation of the iridium complex and concerted cis addition of Ph3MH to the square-planar intermediate. The relative rate of addition of Ph3MH increases in the order Si (1) < Ge (18) < Sn (70) and the difference in rate within experimental error is due entirely to change in ΔS0. It is concluded that, for this particular series of oxidative addition reactions, solvation effects related to a change in polarity on passage to the transition state are more important than bond energies, or acid–base properties, in determining relative reaction energetics. The relevance of entropy barriers to the problem of paraffin activation is discussed.

Synthese von Alkin-, Alkinyl-und Vinyliden-Rhodium-Komplexen ausgehend von Alkinyltriphenylsilanen [1] / Synthesis of Alkyne, Alkynyl and Vinylidene Rhodium Complexes from Alkynyltriphenylsilanes [1]

1994 ◽  
Vol 49 (7) ◽  
pp. 859-869 ◽  
Author(s):  
Matthias Baum ◽  
Bettina Windmüller ◽  
Helmut Werner
Keyword(s):  
Oxidative Addition ◽  
Rhodium Complexes ◽  
Square Planar ◽  
Cyclopentadienyl Complexes

Abstract Compound [RhCl(PiPr3)2]n (1) reacts with RC≡CSiPh3 to give the rhodium(I) complexes trans-[RhCl(RC≡CSiPh3)(PiPr3)2] (2-5) of which 2 (R = CH3) and 5 (R = C6H5) rearrange thermally to yield the vinylidene isomers trans-[RhCl(=C=C(SiPh3)(R)(PiPr3)2] (6,7). The reaction of 2 and 4 (R = CH2OMe) with NaC5H* affords the cyclopentadienyl complexes [C5H5Rh(RC≡CSiPh3)(PiPr3)] (8,9). The square-planar alkynylrhodium(I) compounds trans-[Rh(C≡CSiPh3)(L)(PiPr3)2] (12,13) are obtained from 10 or 11 on treatment with NaN(SiMe3)2; they react with cyclopentadiene to give [C5H5RhH(C≡CSiPh3)(PiPr3)] (14). Five- and six-coordinate bis(alkynyl)hydridorhodium(III) complexes [RhH(C≡CSiPh3)(C≡CSiR3)(PiPr3)2] (15,16) and [RhH(C≡CSiPh3)(C≡CSiR3)(py)(PiPr3)2] (17,18) are prepared from 12 and 13 by oxidative addition of HC≡CSiR3 (R = CH3, C6H5). The reaction of 12 with Me3SiC≡CCO2Et leads to the formation of trans-[Rh(C≡CSiPh3)(Me3SiC≡CCO2Et)(PiPr3)2] (19).

An S4-symmetric mixed-valent decacopper cage comprised of [CuII(L-S2N2)] complexes bridged by CuI(MeCN)n (n = 1 or 2) cations

2016 ◽  
Vol 45 (7) ◽  
pp. 2997-3002 ◽  
Author(s):  
Skylar J. Ferrara ◽  
Bo Wang ◽  
James P. Donahue
Keyword(s):  
Oxidative Addition ◽  
Cage Compound ◽  
Square Planar ◽  
Cuprous Ions

Oxidative addition of 1,2,11,12-tetrathia-5,8,15,19-tetra(N-methylamino)cycloicosane to [Cu(MeCN)4][BF4] yields an S4-symmetric decacopper cage compound with four cupric ions in distorted square planar bis(amino) bis(thiolato) ligand environments bridged by six cuprous ions with MeCN ligands.

scholarly journals Insights into metal–ligand hydrogen transfer: a square-planar ruthenate complex supported by a tetradentate amino–amido-diolefin ligand

2016 ◽  
Vol 52 (36) ◽  
pp. 6138-6141 ◽  
Author(s):  
Demyan E. Prokopchuk ◽  
Alan J. Lough ◽  
Rafael E. Rodriguez-Lugo ◽  
Robert H. Morris ◽  
Hansjörg Grützmacher
Keyword(s):  
Hydrogen Transfer ◽  
Oxidative Addition ◽  
Square Planar ◽  
Elimination Reactions ◽  
Metal Ligand

A unique square planar anionic ruthenium(0) complex with amido and amine donors undergoes rapid NH oxidative addition/elimination reactions.

Highly Diastereoselective Oxidative Addition of Methyl Iodide to a Chiral Square-Planar Complex

2006 ◽  
Vol 45 (17) ◽  
pp. 6559-6561 ◽  
Author(s):  
Mesfin Janka ◽  
Abdurrahman Ç. Atesin ◽  
Daniel J. Fox ◽  
Christine Flaschenriem ◽  
William W. Brennessel ◽  
...  
Keyword(s):  
Methyl Iodide ◽  
Oxidative Addition ◽  
Planar Complex ◽  
Square Planar

scholarly journals (+)-trans-Chlorido{2-[(Rp)-2-(methylsulfanyl)ferrocenyl]-2,5,6,7-tetrahydropyrrolo[1,2-c]imidazol-3-ylidene}bis(triphenylphosphane-κP)palladium(II) hexafluoridophosphate dichloroform disolvate

2016 ◽  
Vol 72 (9) ◽  
pp. 1330-1334 ◽  
Author(s):  
Cody Wilson-Konderka ◽  
Alan J. Lough ◽  
Costa Metallinos
Keyword(s):  
Oxidative Addition ◽  
Coordination Geometry ◽  
Pyrrolidine Ring ◽  
Π Interactions ◽  
Envelope Conformation ◽  
Square Planar ◽  
Complex Features ◽  
Cl Atom

The title solvated complex, [FePd(C5H5)(C12H13N2S)Cl(C18H15P)2]PF6·2CHCl3, bearing a chiral ferrocenyl pyrroloimidazolylideneN-heterocyclic carbene (NHC) ligand, was synthesized by oxidative addition of a chloroimidazolium salt to Pd(PPh3)4. The PdIIion is coordinated in a slightly distorted square-planar coordination geometry, with the Cl atomtransto the coordinating C atom of the pyrroloimidazolylidene ligand. The complex features a pendant thioether group that is not involved in coordination to Pd. In the crystal, weak C—H...F and C—H...π interactions connect the components of the structure, forming chains propagating along [1-10]. The fused pyrrolidine ring is in an envelope conformation, and the flap atom was refined as disordered over two sets of sites, with occupancies of 0.77 (4) and 0.23 (4).

Polyphosphinhaltige Trichlorostannatoplatin(II)-Komplexe: Synthese und NMR(119Sn, 31P)-Charakterisierung / Trichlorostannatoplatinum(II) Complexes Containing Polyphosphines: Synthesis and NMR (119Sn, 31P) Characterization

1986 ◽  
Vol 41 (12) ◽  
pp. 1561-1564 ◽  
Author(s):  
Peter Brüggeller
Keyword(s):  
Nmr Spectroscopy ◽  
Oxidative Addition ◽  
Spin Systems ◽  
H Nmr ◽  
Trigonal Bipyramidal ◽  
Planar Structures ◽  
Square Planar ◽  
Spectral Patterns

AbstractTrichlorostannatoplatinum(II) complexes containing bis(2-diphenylphosphinoethyl)phenyl- phosphine, etp, and the tripod ligand tris(2-diphenylphosphinoethyl)phosphine, PP3, respective­ly, have been prepared and characterized by 119Sn{1H} and 31P{1H} NMR spectroscopy. [(etp)PtCl](BPh4) (1a) reacts with SnCl2 via oxidative addition to give [(etp)PtSnCl3](BPh4) (1b). The 31P NMR spectral patterns of type 1 complexes are consistent with AX2 spin-systems and square planar structures in solution. There is 31P NMR evidence that in the presence of (Ph4P)Cl 1b adds further SnCl2. The possibility of the formation of [(etp)Pt(SnCl3)2] (2) is discussed. [(PP3)PtCl](BPh4) (3a) reacts with SnCl2 to give [(PP3)PtSnCl3](BPh4) (3b). The 31P NMR spec­tral patterns of 3a and 3b are consistent with AX3 spin-systems and trigonal bipyramidal struc­tures.

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