Phosphination of ferrocenium cation with aminophosphines

Chamkin, Aleksandr A.; Krivykh, V. V.; Shtel'Tser, Nikolay A.; Semeikin, Oleg V.; Dolgushin, Fedor M.; Ustynyuk, Nikolai A.

doi:10.1007/s11172-019-2450-2

Cited by 4 publications

(9 citation statements)

References 34 publications

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“…[54] The results obtained in the present study show that M06-L was definitely a good choice for the theoretical analysis of the mechanism of phosphination of ferrocenium carried out in the original papers. [5][6] Because the accurate values of E gas are readily available at the DLPNO-CCSD(T) level, it is possible to give more accurate estimations for ΔG SMD values as well. In this way, the Gibbs free energy values for the compounds are constructed as G SMD = E gas + G corr + E solv , where E gas is obtained at the DLPNO-CCSD(T) level and G corr and E solv are taken from the corresponding M06-L/6-311++G(d,p) calculation (see References [55][56] for more examples of such an approach).…”

Section: Dlpno-ccsd(t) Calculations and Benchmarking Of Dft Functiomentioning

confidence: 99%

“…It was shown recently that ferrocenium reacts with nucleophilic phosphorus compounds PR 3 (namely, tertiary phosphines and aminophosphines) to yield the corresponding ferrocenylphosphonium salts [CpFe(C 5 H 4 PR 3 )] + , that is, this reaction represents a novel approach for C H functionalization of ferrocene. [5][6] At the same time, other nucleophilic reactions of ferrocenium leading to functionalization of the cyclopentadienyl (Cp) ring are extremely rare and their mechanisms remain unclear.…”

Section: Introductionmentioning

confidence: 99%

“…As the phenomenology of the described direct phosphination of ferrocenium is totally new, the investigation of the reaction mechanism is of great importance because it allows enriching the scope of the process. For example, it was shown that the reactions of ferrocenium with secondary phosphines proceed as replacement of the Cp-ring rather than its C H functionalization [7] and the reason for that is not obvious. However, the experimental study of the reaction mechanism is difficult because it involves short-lived odd-electron intermediates.…”

Section: Introductionmentioning

confidence: 99%

“…A possible reaction pathway for the phosphination of ferrocenium was proposed in the original paper and was studied using DFT (M06-L/6-311++G(d,p) level of theory with the continuum solvation model [SMD]) for PMe 3 and PMePh 2 [5] and later for PhP(NMe 2 ) 2 , PhP(NEt 2 ) 2 , Ph 2 P(NMe 2 ), and Ph 2 P(NEt 2 ). [6] However, DFT calculations for organometallic compounds are challenging and some doubts about the reliability of the original study arise. In the present work, we address the following points:…”

Section: Introductionmentioning

confidence: 99%

“…[11] Because of the high computational cost of the whole study, we have limited ourselves to PMe 3 as the phosphorus nucleophile and studied the main reaction pathway along with some side reactions discussed in the original paper. The reaction of ferrocenium with PMe 3 proceeds in the same way as with other phosphorus reactants while the optimization of some structures is not burdened by the choice of a proper conformer (especially for transition states [6] ). Therefore, PMe 3 is a reasonable model nucleophile for the present study.…”

Section: Introductionmentioning

confidence: 99%

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DFT, DLPNO‐CCSD(T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine

Chamkin

Serkova

2020

J Comput Chem

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The reaction between ferrocenium and trimethylphosphine was studied using density functional theory (DFT), domain‐based local pair natural orbital coupled cluster theory with single‐, double‐, and perturbative triple excitations (DLPNO‐CCSD(T)), and N‐electron valence state perturbation theory (NEVPT2). The accuracy of the DFT functionals decreases compared to the DLPNO‐CCSD(T) level in the following order: M06‐L > TPSS > M06, BLYP > PBE, PBE0, B3LYP > > PWPB95 > > DSD‐BLYP. The roles of thermochemical, continuum solvation (SMD), and counterpoise corrections were evaluated. Grimme's D3 empirical dispersion correction is essential for all functionals studied except M06 and M06‐L. The reliability of the frequency calculations performed directly within the SMD was confirmed. The systems showed no significant multireference character according to T1 and T2 diagnostics and the fractional occupation number (FOD) weighted electron density analysis. The multireference NEVPT2 calculations gave qualitatively valid conclusions about the reaction mechanism. However, a multireference approach is generally not recommended because it requires arbitrary chosen active spaces.

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Section: Dlpno-ccsd(t) Calculations and Benchmarking Of Dft Functiomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

DFT, DLPNO‐CCSD(T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine

Chamkin

Serkova

2020

J Comput Chem

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Reactions of Ferrocenium Hexafluorophosphate with P−OR Nucleophiles Give Ring C−H Functionalization or Ring Replacement Products Depending on the Phosphorus Reagent

et al. 2021

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Ferrocenium hexafluorophosphate reacts with different PÀ OR nucleophiles (PR 3 ) in CH 2 Cl 2 at room temperature to give either half-sandwich complexes [CpFe(PR 3 ) 3 ](PF 6 ) (PR 3 =P(OMe) 3 , P-(OEt) 3 , PhP(OMe) 2 ) or ferrocenylphosphonium salts [CpFe (C 5 H 4 PR 3 )](PF 6 ) (PR 3 =iPr 2 P(OMe), iPr 2 P(OEt)). Mixtures of both products are formed for some other nucleophiles (PR 3 =Ph 2 P-(OMe), Ph 2 P(OEt), PhP(OiPr) 2 ). The mechanism of the former reaction was established using DFT calculations. This reaction pathway is especially characteristic of π-acceptor nucleophiles, which is presumably explained by their ability to stabilize the 19e intermediates. The result of the reaction with tertiary phosphines, aminophosphines, and PÀ OR nucleophiles can be reliably predicted based on the values of the Tolman electronic parameter (below 2070 cm À 1 -only ferrocenylphosphonium salt, in between 2073 cm À 1 and 2080 cm À 1 -only half-sandwich complex, and in the range from 2070 cm À 1 to 2073 cm À 1mixtures of both products).

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Assessment of the applicability of DFT methods to [Cp*Rh]‐catalyzed hydrogen evolution processes

Chamkin,

Chamkina

2024

J Comput Chem

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The present computational study provides a benchmark of density functional theory (DFT) methods in describing hydrogen evolution processes catalyzed by [Cp*Rh]‐containing organometallic complexes. A test set was composed of 26 elementary reactions featuring chemical transformations and bonding situations essential for the field, including the emerging concept of non‐innocent Cp* behavior. Reference values were obtained from a highly accurate 3/4 complete basis set and 6/7 complete PNO space extrapolated DLPNO‐CCSD(T) energies. The performance of lower‐level extrapolation procedures was also assessed. We considered 84 density functionals (DF) (including 13 generalized gradient approximations (GGA), nine meta‐GGAs, 33 hybrids, and 29 double‐hybrids) and three composite methods (HF‐3c, PBEh‐3c, and r2SCAN‐3c), combined with different types of dispersion corrections (D3(0), D3BJ, D4, and VV10). The most accurate approach is the PBE0‐DH‐D3BJ (MAD of 1.36 kcal mol−1) followed by TPSS0‐D3BJ (MAD of 1.60 kcal mol−1). Low‐cost r2SCAN‐3c composite provides a less accurate but much faster alternative (MAD of 2.39 kcal mol−1). The widely used Minnesota‐family M06‐L, M06, and M06‐2X DFs should be avoided (MADs of 3.70, 3.94, and 4.01 kcal mol−1, respectively).

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Phosphination of ferrocenium cation with aminophosphines

Cited by 4 publications

References 34 publications

DFT, DLPNO‐CCSD(T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine

DFT, DLPNO‐CCSD(T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine

Reactions of Ferrocenium Hexafluorophosphate with P−OR Nucleophiles Give Ring C−H Functionalization or Ring Replacement Products Depending on the Phosphorus Reagent

Assessment of the applicability of DFT methods to [Cp*Rh]‐catalyzed hydrogen evolution processes

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