Di-μ-iodo-bis[dicarbonylrhodium(I)]

Burger, Sylvain; Therrien, Bruno; Süß‐Fink, Georg

doi:10.1107/s1600536803005439

Cited by 4 publications

(4 citation statements)

References 9 publications

(6 reference statements)

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“…FT-IR spectra of the prepared SILP catalyst (Fig. 1) confirmed the conversion of the dimer [Rh(CO) 2 I] 2 complex to the Monsanto cis-[Rh(CO) 2 I 2 ] 2 complex anion, by the change of the characteristic strong carbonyl stretching bands originating from the dimer (u CO = 2075, 2043, 2028 cm 21 ) 16 to bands assignable to the complex anion at u CO = 2076 and 2006 cm 21 .…”

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confidence: 65%

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

et al. 2006

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confidence: 65%

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

et al. 2006

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“…This conversion is completed within 18 h at T = 60 °C and excess MeI (140 equiv). Compound 6 was independently and quantitatively prepared by reaction of 4 with 1 / 2 equiv of [Rh(CO) 2 I] 2 in CH 2 Cl 2 . These results are in agreement with earlier observations that trans -[Rh(SPANphos)(CO)Cl] complexes do not undergo oxidative additions either and confirms that compound 5 is a monomeric Rh complex containing a trans-spanning ligand which does not isomerize to the cis form in solution (which would in fact lead to MeI oxidative addition)…”

Section: Resultsmentioning

confidence: 99%

“…All glassware was dried prior to use by heating under vacuum. All common solvents and chemicals were commercially available and were purchased from Aldrich Chemical Co. P(SiMe 3 ) 3 , 4,4′-diacetyl- o -terphenyl, [Rh(CO) 2 I] 2 , and 1,3-diphenyl-2-propen-1-one were prepared according to the literature. The Rh precursors were obtained as a generous gift from Umicore AG & Co. Kg (Germany).…”

Section: Methodsmentioning

confidence: 99%

Wide-Bite-Angle Diphosphinines: Design, Synthesis, and Coordination Properties

et al. 2008

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A wide-bite-angle diphosphinine ligand has been designed and synthesized, which exhibits structural features for a preferred formation of trans complexes. Due to the linear orientation of the lone-pair electrons of the phosphorus donors in combination with an appropriate P-P distance, trans coordination toward a Rh center was observed and the corresponding LRh(CO)I complex could be characterized crystallographically. Although typical reactivities usually observed for trans complexes were found, reaction of the diphosphinine with the cis-enforcing precursor [Rh(nbd) 2 ]BF 4 did result in the formation of several species at low temperature, to which cis-structures were attributed.

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“…Methyl iodide (Aldrich) was distilled over calcium hydride and stored in foil-wrapped Schlenk tubes under argon to prevent the formation of I 2 . The starting rhodium precursors [Rh(μ-Cl)(CO) 2 ] 2 ( 1 ) and [Rh(μ-I)(CO) 2 ] 2 ( 2 ) were synthesized according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Reactivity of Rhodium(I) Complexes Bearing Nitrogen-Containing Ligands toward CH₃I: Synthesis and Full Characterization of Neutralcis-[RhX(CO)₂(L)] and Acetyl [RhI(μ-I)(COMe)(CO)(L)]₂Complexes

et al. 2012

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The neutral rhodium(I) square-planar complexes [RhX(CO)(2)(L)] [X = Cl (3), I (4)] bearing a nitrogen-containing ligand L [diethylamine (a), triethylamine (b), imidazole (c), 1-methylimidazole (d), pyrazole (e), 1-methylpyrazole (f), 3,5-dimethylpyrazole (g)] are straightforwardly obtained from L and [Rh(μ-X)(CO)(2)](2) [X = Cl (1), I (2)] precursors. The synthesis is extended to the diethylsulfide ligand h for 3h and 4h. According to the CO stretching frequency of 3 and 4, the ranking of the electronic density on the rhodium center follows the order b > a ≈ d > c > g > f ≈ h > e. The X-ray molecular structures of 3a, 3d-3f, 4a, and 4d-4f were determined. Results from variable-temperature (1)H and (13)C{(1)H} NMR experiments suggest a fluxional associative ligand exchange for 4c-4h and a supplementary hydrogen-exchange process in 4e and 4g. The oxidative addition reaction of CH(3)I to complexes 4c-4g affords the neutral dimeric iodo-bridged acetylrhodium(III) complexes [RhI(μ-I)(COCH(3))(CO)(L)](2) (6c-6g) in very good isolated yields, whereas 4a gives a mixture of neutral 6a and dianionic [RhI(2)(μ-I)(COCH(3))(CO)][NHMeEt(2)](2) and 4h exclusively provides the analogue dianionic complex with [SMeEt(2)](+) as the counterion. X-ray molecular structures for 6d(2) and 6e reveal that the two apical CO ligands are in mutual cis positions, as are the two apical d and e ligands, whereas isomer 6d(1) is centrosymmetric. Further reactions of 6d and 6e with CO or ligand e gave quantitatively the monomeric complexes [RhI(2)(COCH(3))(CO)(2)(d)] (7d) and [RhI(2)(COCH(3))(CO)(e)(2)] (8e), respectively, as confirmed by their X-ray structures. The initial rate of CH(3)I oxidative addition to 4 as determined by IR monitoring is dependent on the nature of the nitrogen-containing ligand. For 4a and 4h, reaction rates similar to those of the well-known rhodium anionic [RhI(2)(CO)(2)](-) species are observed and are consistent with the formation of this intermediate species through methylation of the a and h ligands. The reaction rates are reduced significantly when using imidazole and pyrazole ligands and involve the direct oxidative addition of CH(3)I to the neutral complexes 4c-4g. Complexes 4c and 4d react around 5-10 times faster than 4e-4g mainly because of electronic effects. The lowest reactivity of 4f toward CH(3)I is attributed to the steric effect of the coordinated ligand, as supported by the X-ray structure.

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Di-μ-iodo-bis[dicarbonylrhodium(I)]

Abstract: Key indicatorsSingle-crystal X-ray study T = 153 K Mean '(O±C) = 0.013 A Ê R factor = 0.053 wR factor = 0.141 Data-to-parameter ratio = 18.0 For details of how these key indicators were automatically derived from the article, see

Cited by 4 publications

References 9 publications

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

Wide-Bite-Angle Diphosphinines: Design, Synthesis, and Coordination Properties

Reactivity of Rhodium(I) Complexes Bearing Nitrogen-Containing Ligands toward CH₃I: Synthesis and Full Characterization of Neutralcis-[RhX(CO)₂(L)] and Acetyl [RhI(μ-I)(COMe)(CO)(L)]₂Complexes

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Di-μ-iodo-bis[dicarbonylrhodium(I)]

Abstract: Key indicatorsSingle-crystal X-ray study T = 153 K Mean '(O±C) = 0.013 A Ê R factor = 0.053 wR factor = 0.141 Data-to-parameter ratio = 18.0 For details of how these key indicators were automatically derived from the article, see

Cited by 4 publications

References 9 publications

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

Wide-Bite-Angle Diphosphinines: Design, Synthesis, and Coordination Properties

Reactivity of Rhodium(I) Complexes Bearing Nitrogen-Containing Ligands toward CH3I: Synthesis and Full Characterization of Neutralcis-[RhX(CO)2(L)] and Acetyl [RhI(μ-I)(COMe)(CO)(L)]2Complexes

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Reactivity of Rhodium(I) Complexes Bearing Nitrogen-Containing Ligands toward CH₃I: Synthesis and Full Characterization of Neutralcis-[RhX(CO)₂(L)] and Acetyl [RhI(μ-I)(COMe)(CO)(L)]₂Complexes