Vinylidene carbonylation at a manganese–iron complex: A density functional study of mechanism

Ivanova-Shor, Elena A.; Наслузов, Владимир А.; Shor, Aleksey M.; Antonova, A. B.; Rösch, Notker

doi:10.1016/j.jorganchem.2011.06.051

Cited by 8 publications

(8 citation statements)

References 55 publications

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“…CHPh, 1-PPh3. ɗɧɟɪɝɟɬɢɱɟɫɤɢɣ ɷɮɮɟɤɬ E-Z ɢɡɨɦɟɪɢɢ ɛɨɥɟɟ ɫɤɪɨɦɧɵɣ: 0,5 (ɞɥɹ Eb-Zb) ɢ 1,6 ɤɤɚɥ/ɦɨɥɶ (ɞɥɹ Eɚ-Zɚ), ɱɬɨ ɫɨɝɥɚɫɭɟɬɫɹ ɫɨ ɡɧɚɱɟɧɢɟɦ 0,4 ɤɤɚɥ/ɦɨɥɶ ɞɥɹ ɪɚɡɧɢɰɵ ɷɧɟɪɝɢɣ ɢɡɨɦɟɪɨɜ 2ȿ-ɋɈ ɢ 2Z-ɋɈ ɞɢɤɚɪɛɨɧɢɥɶɧɨɝɨ ɤɨɦɩɥɟɤɫɚ Cp(CO) 2 MnFe(P-C=CHPh)(CO) 4 ɜ ɧɚɲɢɯ ɩɪɟɞɵɞɭɳɢɯ Ɏɉ-ɪɚɫɱɟɬɚɯ [ 9 ]. ȼɫɟ ɢɡɨɦɟɪɵ ɤɨɦɩɥɟɤɫɚ 2-PPh3 ɢɦɟɸɬ ɩɪɚɤɬɢɱɟɫɤɢ ɩɥɨɫɤɢɣ ɰɟɧɬɪɚɥɶɧɵɣ ɦɟɬɚɥɥ-ɜɢɧɢɥɢɞɟɧɨɜɵɣ ɮɪɚɝɦɟɧɬ MnFe(P-C=C), ɫɭɦɦɚ ɭɝɥɨɜ ɩɪɢ sp 2 -ɝɢɛɪɢɞɢɡɨɜɚɧɧɨɦ ɚɬɨɦɟ C 1 ɫɨɫɬɚɜɥɹɟɬ 359,5-360q.…”

Section: ɋɢɫ 2 ɉɩɬɢɦɢɡɢɪɨɜɚɧɧɵɟ ɦɟɬɨɞɨɦ B3lyp ɫɬɪɭɤɬɭɪɵ ɢɡɨɦɟɪɨɜ ɛɢɹɞ...unclassified

“…ȼɟɥɢɱɢɧɵ ɭɝɥɨɜ ɜɨɤɪɭɝ ɚɬɨɦɚ ɋ 1 ɡɚɦɟɬɧɨ ɨɬɥɢɱɚɸɬɫɹ ɨɬ 120q: ɭɝɨɥ Mn-C 1 -Fe ɫɨɫɬɚɜɥɹɟɬ 88-91q, ɬɨɝɞɚ ɤɚɤ ɭɝɥɵ Mn-C 1 -C 2 ɢ Fe-C 1 -C 2 ɜɚɪɶɢɪɭɸɬɫɹ ɜ ɢɧɬɟɪɜɚɥɚɯ 131-146q ɢ 123-138q ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. Ⱥɧɚɥɨɝɢɱɧɨ ɝɟɤɫɚɤɚɪɛɨɧɢɥɶɧɨɦɭ ɤɨɦɩɥɟɤɫɭ 2Z-ɋɈ [ 9 ], ɪɚɡɧɢɰɚ ɭɝɥɨɜ Mn-C 1 -C 2 ɢ Fe-C 1 -C 2 ɜ Z-ɢɡɨɦɟɪɚɯ 2Zɚ-PPh3 ɢ 2Zb-PPh3 ɧɟ ɩɪɟɜɵɲɚɟɬ 6q. ȼ E-ɢɡɨɦɟɪɚɯ 2E-CO ɢ 2Eb-PPh3 ɭɝɨɥ Mn-C 1 -C 2 ɛɨɥɟɟ ɱɟɦ ɧɚ 12q ɩɪɟɜɵɲɚɟɬ ɭɝɨɥ Fe-C 1 -C 2 .…”

Section: ɋɢɫ 2 ɉɩɬɢɦɢɡɢɪɨɜɚɧɧɵɟ ɦɟɬɨɞɨɦ B3lyp ɫɬɪɭɤɬɭɪɵ ɢɡɨɦɟɪɨɜ ɛɢɹɞ...unclassified

“…Ɉɫɧɨɜɧɵɟ ɨɬɥɢɱɢɹ ɜ ɫɬɪɨɟɧɢɢ ɢɡɨɦɟɪɨɜ ɜɵɡɜɚɧɵ ɩɟɪɟɦɟɧɨɣ ɦɟɫɬɚɦɢ ɥɢɝɚɧɞɨɜ ɩɪɢ ɚɬɨɦɟ Mn ɢ ɡɚɤɥɸɱɟɧɵ ɜ ɫɬɪɭɤɬɭɪɟ ɬɪɟɭɝɨɥɶɧɢɤɚ Mn-C 1 -Fe. ɇɚɢɛɨɥɟɟ ɫɭɳɟɫɬɜɟɧɧɨɟ ɪɚɫɯɨɠɞɟɧɢɟ ɧɚɛɥɸɞɚɟɬɫɹ ɜ ɪɚɫɫɱɢɬɚɧɧɨɣ ɞɥɢɧɟ ɫɜɹɡɢ Mn-Fe, ɤɨɬɨɪɚɹ ɜ PPh 3 -ɤɨɦɩɥɟɤɫɚɯ ɬɢɩɚ b ɫɨɫɬɚɜɢɥɚ 2,85 Å, ɱɬɨ ɧɚ a0,1 Å ɛɨɥɶɲɟ, ɱɟɦ ɜ PPh 3 -ɢɡɨɦɟɪɚɯ ɬɢɩɚ a, 2Eɚ-PPh3 ɢ 2Zɚ-PPh3 (2,76-2,77 Å), ɚ ɬɚɤɠɟ ɜ ɝɟɤɫɚɤɚɪɛɨɧɢɥɶɧɵɯ ɤɨɦɩɥɟɤɫɚɯ 2-CO (2,74-2,75 Å) [ 9 ]. ɂɧɬɟɪɟɫɧɨ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɬɚɤɨɟ ɪɚɫɫɬɨɹɧɢɟ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɜɟɪɯɧɟɣ ɝɪɚɧɢɰɟ ɬɢɩɢɱɧɵɯ ɞɥɢɧ ɫɜɹɡɟɣ ɦɟɬɚɥɥ-ɦɟɬɚɥɥ ɜ ɛɢɹɞɟɪɧɵɯ ɤɨɦɩɥɟɤɫɚɯ MnFe, 2,70-2,85 Å [ 1, 4 ].…”

Section: ɋɢɫ 2 ɉɩɬɢɦɢɡɢɪɨɜɚɧɧɵɟ ɦɟɬɨɞɨɦ B3lyp ɫɬɪɭɤɬɭɪɵ ɢɡɨɦɟɪɨɜ ɛɢɹɞ...mentioning

confidence: 99%

“…Ɋɟɚɤɰɢɹ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɞɢɤɚɪɛɨɧɢɥɶɧɨɝɨ ɤɨɦɩɥɟɤɫɚ Cp(CO) 2 Mn=C=CHPh (1-ɋɈ) ɫ Fe 2 (CO) 9 ɪɚɧɟɟ ɛɵɥɚ ɧɚɦɢ ɞɟɬɚɥɶɧɨ ɢɡɭɱɟɧɚ ɦɟɬɨɞɨɦ ɮɭɧɤɰɢɨɧɚɥɚ ɩɥɨɬɧɨɫɬɢ (Ɏɉ) [ 9 ]. Ȼɵɥɨ ɩɨɤɚɡɚɧɨ, ɱɬɨ ɞɜɚ ɢɡɨɦɟɪɚ ɢɧɬɟɪɦɟɞɢɚɬɚ 2-ɋɈ ɢ ɤɨɦɩɥɟɤɫ 3-ɋɈ ɢɦɟɸɬ ɢɞɟɧɬɢɱɧɵɟ ɷɧɟɪɝɢɢ.…”

mentioning

confidence: 99%

“…ȼ ɪɚɫɱɟɬɚɯ ɛɵɥɢ ɢɫɩɨɥɶɡɨɜɚɧɵ ɫɥɟɞɭɸɳɢɟ ɩɨɥɧɨɷɥɟɤɬɪɨɧɧɵɟ ɛɚɡɢɫɧɵɟ ɧɚɛɨɪɵ triple-] ɤɚɱɟɫɬɜɚ [ 18 ] Ⱦɥɹ ɨɰɟɧɤɢ ɨɬɧɨɫɢɬɟɥɶɧɵɯ ɷɧɟɪɝɢɣ ɢɡɨɦɟɪɨɜ ɢɫɩɨɥɶɡɨɜɚɧɵ ɷɥɟɤɬɪɨɧɧɵɟ ɷɧɟɪɝɢɢ 'E. ɍɱɟɬ ɷɧɬɚɥɶɩɢɣɧɵɯ ɢ ɷɧɬɪɨɩɢɣɧɵɯ ɜɤɥɚɞɨɜ ɧɟ ɩɪɨɜɨɞɢɥɫɹ, ɩɨɫɤɨɥɶɤɭ ɨɠɢɞɚɟɬɫɹ, ɱɬɨ ɢɯ ɜɤɥɚɞ ɞɥɹ ɪɟɚɤɰɢɣ, ɩɪɨɬɟɤɚɸɳɢɯ ɛɟɡ ɢɡɦɟɧɟɧɢɹ ɱɢɫɥɚ ɪɟɚɝɟɧɬɨɜ, ɧɟ ɩɪɟɜɵɫɢɬ 2 ɤɤɚɥ/ɦɨɥɶ [ 9 ]. ɋɬɪɭɤɬɭɪɵ ɢ ɷɧɟɪɝɢɢ ɤɨɦɩɥɟɤɫɨɜ ɛɵɥɢ ɪɚɫɫɱɢɬɚɧɵ ɛɟɡ ɭɱɟɬɚ ɫɨɥɶɜɚɬɚɰɢɨɧɧɵɯ ɷɮɮɟɤɬɨɜ.…”

unclassified

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A QUANTUM CHEMICAL STUDY OF THE EFFECT OF PHOSPHINE LIGAND ON THE STRUCTURE OF THE Mn AND Fe VINYLIDENE BINUCLEAR COMPLEX

2016

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Ɇɟɬɨɞɨɦ ɮɭɧɤɰɢɨɧɚɥɚ ɩɥɨɬɧɨɫɬɢ B3LYP ɜɵɩɨɥɧɟɧɵ ɪɚɫɱɟɬɵ ɫɬɪɭɤɬɭɪɵ ɢ ɨɬɧɨɫɢɬɟɥɶɧɨɣ ɷɧɟɪɝɢɢ ɛɢɹɞɟɪɧɵɯ ɠɟɥɟɡɨ-ɦɚɪɝɚɧɰɟɜɵɯ ɤɨɦɩɥɟɤɫɨɜ ɫ ɮɨɫɮɢɧɨɜɵɦ ɥɢɝɚɧɞɨɦ L, ɫɭɳɟɫɬɜɭɸɳɢɯ ɜ ɜɢɧɢɥɢɞɟɧɨɜɨɣ Cp(CO)(L)MnFe(P-C=CHPh)(CO) 4 (2) ɢ ɛɟɧɡɢɥɢɞɟɧɤɟɬɟɧɨɜɨɣ K 4 -{C[Mn(CO)(L)Cp](CO)CHPh}Fe(CO) 3 (3) ɮɨɪɦɚɯ. Ⱦɥɹ ɤɚɠɞɨɣ ɢɡ ɮɨɪɦ ɪɚɫɫɦɨɬɪɟɧɵ ɩɨ ɱɟɬɵɪɟ ɢɡɨɦɟɪɚ, ɨɬɥɢɱɚɸɳɢɟɫɹ ɩɨɥɨɠɟɧɢɟɦ ɥɢɝɚɧɞɚ L ɨɬɧɨɫɢɬɟɥɶɧɨ ɮɟɧɢɥɶɧɨɝɨ ɤɨɥɶɰɚ (ɤɨɧɮɨɪɦɟɪɵ a ɢ b) ɢ ɡɚɦɟɫɬɢɬɟɥɹ Ph ɨɬɧɨɫɢɬɟɥɶɧɨ ɫɜɹɡɢ ɋ=ɋ (ɤɨɧɮɨɪɦɟɪɵ E ɢ Z), ɢ ɨɩɪɟɞɟɥɟɧɚ ɢɯ ɨɬɧɨɫɢɬɟɥɶɧɚɹ ɫɬɚɛɢɥɶɧɨɫɬɶ. ɉɨɤɚɡɚɧɨ, ɱɬɨ ɜɫɟ ɢɡɨɦɟɪɵ ɮɨɪɦɵ 2 ɢɦɟɸɬ ɩɪɢɦɟɪɧɨ ɨɞɢɧɚɤɨɜɭɸ ɷɧɟɪɝɢɸ (ɜ ɩɪɟɞɟɥɚɯ 4 ɤɤɚɥ/ɦɨɥɶ), ɬɨɝɞɚ ɤɚɤ ɷɧɟɪɝɢɢ ɢɡɨɦɟɪɨɜ ɮɨɪɦɵ 3 ɨɬɥɢɱɚɸɬɫɹ ɜ ɩɪɟɞɟɥɚɯ 21 ɤɤɚɥ/ɦɨɥɶ. ɇɚɢɛɨɥɟɟ ɷɧɟɪɝɟɬɢɱɟɫɤɢ ɜɵɝɨɞɧɵɦ ɹɜɥɹɟɬɫɹ ɢɡɨɦɟɪ 3Ea, ɜ ɤɨɬɨɪɨɦ ɥɢɝɚɧɞ PPh 3 ɧɚɯɨɞɢɬɫɹ ɜ ɤɨɧɬɚɤɬɟ ɫ ɮɟɧɢɥɶɧɵɦ ɡɚɦɟɫɬɢɬɟɥɟɦ ɜɢɧɢɥɢɞɟɧɨɜɨɣ ɝɪɭɩɩɵ. ɍɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ ɫ ɪɨɫɬɨɦ ɪɚɡɦɟɪɚ ɥɢɝɚɧɞɚ L ɜ ɪɹɞɭ PH 3 < PH 2 Ph < PHPh 2 < PPh 3 ɞɥɢɧɚ ɫɜɹɡɢ Mn-P ɭɜɟɥɢɱɢɜɚɟɬɫɹ ɞɨ 2,37 Å ɜ ɫɚɦɨɦ ɫɬɚɛɢɥɶɧɨɦ ɢɡɨɦɟɪɟ ɮɨɪɦɵ 3 ɢ ɞɨ 2,43 Å ɜ ɢɡɨɦɟɪɚɯ ɮɨɪɦɵ 2 ɢ ɬɪɟɯ ɤɨɧɮɨɪɦɟɪɚɯ ɮɨɪɦɵ 3. Ȼɨɥɟɟ ɫɭɳɟɫɬɜɟɧɧɨɟ ɭɜɟɥɢɱɟɧɢɟ ɞɥɢɧɵ ɫɜɹɡɢ Mn-P ɜ ɤɨɦɩɥɟɤɫɚɯ 2 ɢ 3 ɤɨɪɪɟɥɢɪɭɟɬ ɫ ɢɯ ɦɟɧɶɲɟɣ ɫɬɚɛɢɥɶɧɨɫɬɶɸ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɢɡɨɦɟɪɨɦ Ea ɮɨɪɦɵ 3, ɱɬɨ ɫɨɝɥɚɫɭɟɬɫɹ ɫ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦɢ ɞɚɧɧɵɦɢ ɨ ɩɪɢɫɭɬɫɬɜɢɢ ɜ ɪɚɫɬɜɨɪɟ ɬɨɥɶɤɨ ɨɞɧɨɝɨ ɤɨɧɮɨɪɦɟɪɚ 3Ea.

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Section: ɋɢɫ 2 ɉɩɬɢɦɢɡɢɪɨɜɚɧɧɵɟ ɦɟɬɨɞɨɦ B3lyp ɫɬɪɭɤɬɭɪɵ ɢɡɨɦɟɪɨɜ ɛɢɹɞ...unclassified

Section: ɋɢɫ 2 ɉɩɬɢɦɢɡɢɪɨɜɚɧɧɵɟ ɦɟɬɨɞɨɦ B3lyp ɫɬɪɭɤɬɭɪɵ ɢɡɨɦɟɪɨɜ ɛɢɹɞ...mentioning

confidence: 99%

mentioning

confidence: 99%

unclassified

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Synthesis of Cyclic Vinylidene Complexes and Azavinylidene Complexes by Formal [4+2] Cyclization Reactions

Chen

Huang

Lü

et al. 2016

Chemistry A European J

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Reactions of the hydrido-butenylcarbyne complex [OsHCl2(≡CC(PPh3)=CHEt)(PPh3)2]BF4 (1) with nitriles RC≡N (R=2-cyclopropyl-2-oxopropyl, 3-amino-2-oxobutyl) lead to six-membered cyclic vinylidene complexes 3 and azavinylidene complexes 4, that is, iso-osmapyridiniums. Treatment of 1 with excess 2-formylbenzonitrile at reflux temperature in CHCl3 in the presence of air produces a fused osmapyridinium 8, which is first oxidized to the tricyclic iso-osmapyridinium derivative 7, then to iso-osmapyridinium 9, which contains a fused naphthalenone fragment. The conversion of iso-osmapyridinium 9 (with a vinylidene segment) to the iso-osmapyridinium compounds 10 and 11 (with azavinylidene segments) was achieved in the presence of a hydrogen halide, such as HCl or HI. The molecular structures of the complexes synthesized were confirmed by X-ray studies. Moreover, the aromatic stabilization energy and nucleus-independent chemical-shift values of the osmapyridiniums and the strain in the iso-osmapyridinium rings were investigated by DFT calculations.

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Complexes of Group 7 Metals with Metal-Carbon Sigma and Multiple Bonds

Jia

2022

Comprehensive Organometallic Chemistry IV

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Vinylidene carbonylation at a manganese–iron complex: A density functional study of mechanism

Cited by 8 publications

References 55 publications

A QUANTUM CHEMICAL STUDY OF THE EFFECT OF PHOSPHINE LIGAND ON THE STRUCTURE OF THE Mn AND Fe VINYLIDENE BINUCLEAR COMPLEX

A QUANTUM CHEMICAL STUDY OF THE EFFECT OF PHOSPHINE LIGAND ON THE STRUCTURE OF THE Mn AND Fe VINYLIDENE BINUCLEAR COMPLEX

Synthesis of Cyclic Vinylidene Complexes and Azavinylidene Complexes by Formal [4+2] Cyclization Reactions

Complexes of Group 7 Metals with Metal-Carbon Sigma and Multiple Bonds

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