Synthesis and characterization of acetamidine rhodium(III) cationic methyl complex, trans-[Rh(Acac)(PPh3)2(CH3){NHC(NH2)CH3}][BPh4], produced by ammination of acetonitrile ligand in trans-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4]

Shestakova, Elizaveta P.; Varshavsky, Yu.S.; Khrustalev, Victor N.; Смирнов, С. Н.

doi:10.1016/j.jorganchem.2013.03.015

Cited by 5 publications

(2 citation statements)

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“…Thereafter, nucleophilic attack of the coordinated imidazolyl phosphine ligand on the metal-bound acetonitrile results in the generation of the [Ir-I 3 ] product. Such a nucleophilic attack of ligands possessing NH groups to CH 3 CN–M fragments generating an amidine moiety have been previously reported for Ir , as well as various other metals. − …”

Section: Resultssupporting

confidence: 54%

Comparing Square-Planar Rh^I and Ir^I: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity

et al. 2022

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A series of low-valent square-planar Rh complexes [ LH Rh][X] (X = PF6, Br, Cl, I) bearing two protic imidazolyl phosphines (one κ2) and a CO ligand were synthesized and fully characterized. A comparison of the CO stretching frequencies with those of the previously reported [ LH Ir][X] complexes indicates a much lower electron density at the Rh centers. This lower electron density at Rh results in a lower propensity to undergo ligand to metal proton transfer, and in contrast to observations with Ir, the [ LH Rh][X] complexes (X = Cl, Br, I) do not equilibrate with their metal-protonated congeners. Furthermore, the weaker bond strengths of Rh complexes compared to Ir lead to an increased degree of fluxionality in the former, along with a difference in reactivity with hydrogen (H2) and iodine (I2).

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Section: Resultssupporting

confidence: 54%

Comparing Square-Planar Rh^I and Ir^I: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity

et al. 2022

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“…By analogy to our system, the in situ formed acetamidine coordinated to the transition metal ion used. 35–43 The reaction described in Scheme 3 implies the presence of ammonia in the reaction systems. The formation of ammonia has been observed previously.…”

Section: Methodsmentioning

confidence: 99%

Piperidine and piperazine analogs in action: zinc(ii)-mediated formation of amidines

Podjed,

Košmrlj,

Modec

2024

New J. Chem.

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Rhodium(III) cationic methyl complexes containing dimethylformamide ligand, cis-[Rh(β-diket)(PPh3)2(CH3)(DMF)][BPh4] (β-diket = acetylacetonate or benzoylacetonate), in comparison with their acetonitrile analogs

Shestakova

Varshavsky

Khrustalev

et al. 2014

Journal of Organometallic Chemistry

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Synthesis and characterization of acetamidine rhodium(III) cationic methyl complex, trans-[Rh(Acac)(PPh3)2(CH3){NHC(NH2)CH3}][BPh4], produced by ammination of acetonitrile ligand in trans-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4]

Cited by 5 publications

References 12 publications

Comparing Square-Planar Rh^I and Ir^I: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity

Comparing Square-Planar Rh^I and Ir^I: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity

Piperidine and piperazine analogs in action: zinc(ii)-mediated formation of amidines

Rhodium(III) cationic methyl complexes containing dimethylformamide ligand, cis-[Rh(β-diket)(PPh3)2(CH3)(DMF)][BPh4] (β-diket = acetylacetonate or benzoylacetonate), in comparison with their acetonitrile analogs

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Synthesis and characterization of acetamidine rhodium(III) cationic methyl complex, trans-[Rh(Acac)(PPh3)2(CH3){NHC(NH2)CH3}][BPh4], produced by ammination of acetonitrile ligand in trans-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4]

Cited by 5 publications

References 12 publications

Comparing Square-Planar RhI and IrI: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity

Comparing Square-Planar RhI and IrI: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity

Piperidine and piperazine analogs in action: zinc(ii)-mediated formation of amidines

Rhodium(III) cationic methyl complexes containing dimethylformamide ligand, cis-[Rh(β-diket)(PPh3)2(CH3)(DMF)][BPh4] (β-diket = acetylacetonate or benzoylacetonate), in comparison with their acetonitrile analogs

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Comparing Square-Planar Rh^I and Ir^I: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity

Comparing Square-Planar Rh^I and Ir^I: Metal–Ligand Proton Tautomerism, Fluxionality, and Reactivity