Stereoselective oxidative addition of silanes and hydrogen halides to the iridium(I) cis phosphine complexes IrX(CO)(dppe) (X = Br, CN; dppe = 1,2-bis(diphenylphosphino)ethane)

1985 ◽  
Vol 107 (23) ◽  
pp. 6531-6540 ◽  
Author(s):  
Curtis E. Johnson ◽  
Richard Eisenberg
Keyword(s):  
Oxidative Addition ◽  
Hydrogen Halides ◽  
Phosphine Complexes

scholarly journals DFT Study on the Oxidative Addition of 4-Substituted Iodobenzenes on Pd(0)-Phosphine Complexes

2015 ◽  
Vol 2015 ◽  
pp. 1-6 ◽  
Author(s):  
Tímea R. Kégl ◽  
László Kollár ◽  
Tamás Kégl
Keyword(s):  
Free Energy ◽  
Dissociation Energy ◽  
Linear Correlation ◽  
Oxidative Addition ◽  
Dft Study ◽  
Solvation Effect ◽  
Dispersion Correction ◽  
Phosphine Complexes ◽  
Hammett Constants ◽  
Reaction Free Energy

The oxidative addition of 4-substituted iodobenzenes on Pd(0)-PMe3 complexes has been studied at the BP86 level of theory including dispersion correction and solvation effect, with tetrahydrofuran as solvent. The bisphosphine pathway was found to be barrierless, whereas the monophosphine route is hampered by the high dissociation energy of trimethylphosphine. The reaction free energy of this step shows linear correlation with the Hammett constants of the para substituents with the most electron withdrawing groups being the most exergonic.

Preparation of hydrido(vinyl)iridium(III) complexes from functionalized olefins by C—H activation

2006 ◽  
Vol 84 (2) ◽  
pp. 205-213 ◽  
Author(s):  
Bernd Papenfuhs ◽  
Thomas Dirnberger ◽  
Helmut Werner
Keyword(s):  
Key Words ◽  
Oxidative Addition ◽  
Metal Center ◽  
Addition Reactions ◽  
Phosphine Complexes

The four-coordinate iridium(I) precursor trans-[IrCl(N2)(PPh3)2] (1) reacts with functionalized olefins RCH=C(R′)C(O)R′′ by displacement of the dinitrogen ligand and oxidative addition of the C—H bond to the metal center to give six-coordinate hydrido(vinyl)iridium(III) complexes [IrH(Cl){κ2(C,O)-C(R)=C(R′)C(R′′)=O}(PPh3)2] (2–12) in good to excellent yields. The reaction of [IrH(Cl){κ2(C,O)-CH=CHC(Me)=O}(PPh3)2] (2) with AgClO4 affords the cationic compound [IrH{κ2(C,O)-CH=CHC(Me)=O}(PPh3)2]ClO4 (15), which in solution equilibrates with the uncharged isomers [IrH(OClO3){κ2(C,O)-CH=CHC(Me)=O}(PPh3)2] (15a and 15b). In contrast, five-coordinate [IrH{κ2(C,O)-CH=CHC(Et)=O}(PPh3)2]ClO4 (16), prepared from 3 and AgClO4, is stable and undergoes addition reactions with CO, PPh3, C2H4, CH3C≡CH, MeCN, and PhCN to give the six-coordinate complexes [IrH(L){κ2(C,O)-CH=CHC(Et)=O}(PPh3)2]ClO4 (17–22). The neutral hydrido(thiolato) compound [IrH(SPh){κ2(C,O)-CH=CHC(Et)=O}(PPh3)2] (23) was obtained on treatment of 21 with NaSPh. Key words: iridium, C—H activation, hydrido complexes, vinyl complexes, phosphine complexes.

Oxidative addition of triorganostannanes to amine, phosphite and phosphine complexes of platinum

1981 ◽  
Vol 210 (1) ◽  
pp. 121-133 ◽  
Author(s):  
Joaquim F. Almeida ◽  
Hormoz Azizian ◽  
Colin Eaborn ◽  
Alan Pidcock
Keyword(s):  
Oxidative Addition ◽  
Phosphine Complexes

scholarly journals Peripherally-metallated porphyrins: meso-η1-porphyrinyl-platinum(II) complexes of 5,15-diaryl- and 5,10,15-triarylporphyrins

2002 ◽  
Vol 06 (11) ◽  
pp. 695-707 ◽  
Author(s):  
Regan D. Hartnell ◽  
Alison J. Edwards ◽  
Dennis P. Arnold
Keyword(s):  
Oxidative Addition ◽  
Building Blocks ◽  
Molecular Structures ◽  
Porphyrin Ring ◽  
Tertiary Phosphine ◽  
X Ray ◽  
Ring Carbon ◽  
X Ray Crystallography ◽  
Phosphine Complexes ◽  
Organolithium Reagents

Attempted metathesis reactions of peripherally-metallated meso-η1-porphyrinylplatinum(II) complexes such as trans-[ PtBr ( NiDPP )( PPh 3)2]( H 2 DPP = 5,15- diphenylporphyrin ) with organolithium reagents fail due to competitive addition at the porphyrin ring carbon opposite to the metal substituent. This reaction can be prevented by using 5,10,15-triarylporphyrins, e.g. 5,10,15-triphenylporphyrin ( H 2 TrPP ) and 5-phenyl-10,20-bis(3′,5′-di-t-butylphenyl)porphyrin ( H 2 DAPP ) as substrates. These triarylporphyrins are readily prepared using the method of Senge and co-workers by addition of phenyllithium to the appropriate 5,15-diarylporphyrins, followed by aqueous protolysis and oxidation. They are convenient, soluble building blocks for selective substitutions and subsequent transformations at the remaining free meso carbon. The sequence of bromination, optional central metallation and oxidative addition of Pt (0) tris(phosphine) complexes generates the organoplatinum porphyrins in high overall yields. The bromo ligand on the Pt (II) centre can be substituted by alkynyl nucleophiles, including 5-ethynyl NiDPP , to form the first examples of meso-η1-porphyrinylplatinum(II) complexes with a second Pt - C bond. The range of porphyrinylplatinum(II) bis(tertiary phosphine) complexes was extended to the triethylphosphine analogues, by oxidative addition of H 2 TrPPBr to Pt ( PEt 3)3, and the initially-formed cis adduct is only slowly thermally transformed to trans-[ PtBr ( H 2 TrPP )( PEt 3)2]16. The molecular structures of NiDAPP 9b, trans-[ Pt ( NiDPP )( C 2 NiDPP )( PPh 3)2]14 and 16 were determined by X-ray crystallography.

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