Kinetics of reactions of methyl iodide with four-coordinated iridium(I) complexes

Kubota, Mitsuru; Kiefer, Gebhard; Ishikawa, Ryuichi; Bencala, Kenneth E.

doi:10.1016/s0020-1693(00)94811-4

Cited by 24 publications

(7 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…One reasonable possibility is that an SN2 process occurs to give an unstable intermediate (eq 4). Indeed, 1 + 5 -PhCHFCH(C02Et)IrCl(C0)L2+Br -9 FIrCl(CO)L2+Br" + PhCH=CHC02Et (4) on treatment of adduct 6 with AgPF6, which precipitates AgBr and hence should lead to the hypothesized intermediate 9, ethyl frattv-cinnamate is indeed formed. The Ir-containing product exhibits a 19F signal of similar appearance to, but different chemical shift from, that of the side product of the oxidative addition reaction.…”

Section: Resultsmentioning

confidence: 99%

“…Found: C, 29.17; , 4.19; Br, 13.13; Cl, 5.74; F, 3.00. Bromo(l-(carboethoxy)-2-fluoro-2-phenylethyl)carbonylcbIorobis(trimethylphosphine)iridium(III) (6). A solution of 130 mg of 5a in 1 mL of CH2C12 was added to 125 mg of la; after the yellow color faded (several minutes), evaporation of volatiles and trituration with hexane gave 6 as a white powder (130 mg, 60%) which was recrystallized from CH2Cl2-ligroin: mp 136-138 °C; IR (Nujol) 2041 (C=0), 1705 (ester C=0), 310 cm"1 (Ir-Cl).…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Mechanistic studies of oxidative addition to low-valent metal complexes. Stereochemistry at carbon in addition of alkyl halides to iridium(I)

Labinger¹,

Osborn²

1980

Inorg. Chem.

View full text Add to dashboard Cite

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Mechanistic studies of oxidative addition to low-valent metal complexes. Stereochemistry at carbon in addition of alkyl halides to iridium(I)

Labinger¹,

Osborn²

1980

Inorg. Chem.

View full text Add to dashboard Cite

“…Ugo and co-workers have noted that substantial negative Δ S ⧧ values are not inconsistent with a concerted mechanism since considerable distortion of the complex is required at the transition state. However, studies have established large negative Δ S ⧧ values for oxidative addition reaction proceeding by the S N 2 mechanism, and considerably less negative Δ S ⧧ values for reactions proceeding by a concerted mechanism. , The concerted pathway for oxidative addition does not lead to a highly polar species and hence there is not as large a decrease in solvent entropy on approaching the transition state. Δ S ⧧ values of −156 and −114 J mol -1 K -1 in benzene and acetone, respectively, were found for the oxidative addition of MeI to [PtPh 2 (bpy)] by an S N 2 type mechanism .…”

Section: Activation Parameters and Mechanism Of Reactionmentioning

confidence: 99%

Rapid Reversible Oxidative Addition of Group 14−Halide Bonds to Platinum(II): Rates, Equilibria, and Bond Energies

Levy

Puddephatt

1997

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The reversible oxidative addition reactions of methyl(halogeno)tin and methyl(halogeno)germanium compounds to electron-rich platinum(II) complexes of the type [PtMe2(diimine)] have been studied. Complete kinetic and thermodynamic parameters have been obtained by VT 1H NMR for the reversible oxidative addition of Me3EX (E = Sn, X = Cl, Br, I) to [PtMe2(bpy- t bu2)] (bpy- t bu2 = 4,4‘-di-tert -butyl-2,2‘-bipyridyl) and related compounds, while partial data have been obtained for the reductive elimination of Me2SnCl2 from [PtClMe2(Me2SnCl)(bpy- t bu2)] and for the oxidative addition of Me3GeCl to [PtMe2(bpy- t bu2)]. UV−visible spectroscopic studies have also yielded equilibrium constants and ΔG° for the reversible oxidative addition reactions of Me3SnX (X = Cl, Br, I) to [PtMe2(diimine)]. Thermodynamic studies quantitatively establish the halogen effect on the oxidative addition reactions studied according to the favorability series I > Br > Cl. Kinetic studies clearly point to an SN2 mechanism for the reactions studied, and this is further supported by the observation of the cationic complex [PtMe2(Me3Sn)(bpy- t bu2){OC(CD3)2}]+ at low temperature in acetone-d 6. Extremely large second-order rate constants are observed for the oxidative addition of Sn−X bonds to dimethylplatinum(II) complexes, some being greater than 108 M-1 s-1, and it is established that rates follow the series Sn > Ge > Si > C and I > Br > Cl. Estimates have been made of the Pt−MMe3 bond dissociation energies for [PtXMe2(MMe3)(bpy- t bu2)], X = halide, and these are 233, 182, and 172 kJ mol-1 for M = Si, Ge, and Sn, respectively; the values are useful in rationalizing the chemistry of the Pt−M bonds.

show abstract

“…1975, 102, 167. (9) Gill, T. P.; Mann, K. R. Organometallics 1982, 1, 485. (10) McNair, A. M.; Schrenk, J. L.; Mann, K. R. Inorg.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of mixed-ligand cyclopentadienyl-pyrazolylborate complexes of ruthenium

1986

View full text Add to dashboard Cite

Kinetics of reactions of methyl iodide with four-coordinated iridium(I) complexes

Cited by 24 publications

References 32 publications

Mechanistic studies of oxidative addition to low-valent metal complexes. Stereochemistry at carbon in addition of alkyl halides to iridium(I)

Mechanistic studies of oxidative addition to low-valent metal complexes. Stereochemistry at carbon in addition of alkyl halides to iridium(I)

Rapid Reversible Oxidative Addition of Group 14−Halide Bonds to Platinum(II): Rates, Equilibria, and Bond Energies

Synthesis and characterization of mixed-ligand cyclopentadienyl-pyrazolylborate complexes of ruthenium

Contact Info

Product

Resources

About