DFT Study on the Mechanism of Iron-Catalyzed Diazocarbonylation

被引：1

作者：

Kegl, Timea R. ^{[1
,2
,4
]}

Kollar, Laszlo ^{[1
,2
,3
,4
]}

Kegl, Tamas ^{[1
,2
,4
]}

机构：

[1] Univ Pecs, Dept Inorgan Chem, H-7624 Pecs, Hungary

[2] Univ Pecs, MTA PTE Res Grp Select Chem Synth, H-7624 Pecs, Hungary

[3] Univ Pecs, Janos Szentagothai Res Ctr, H-7624 Pecs, Hungary

[4] Ifjusag Utja 6, H-7624 Pecs, Hungary

来源：

MOLECULES | 2020年 / 25卷 / 24期

关键词：

iron-carbonyls; diazocarbonylation; DFT; ETHYL DIAZOACETATE; CARBON-MONOXIDE; SELECTIVE CARBONYLATION; ACCEPTOR PROPERTIES; KETENE CHEMISTRY; NATURAL ORBITALS; COMPLEXES; CARBENE; LIGANDS; VALENCE;

D O I：

10.3390/molecules25245860

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

The mechanism of the carbonylation of diazomethane in the presence of iron-carbonyl-phosphine catalysts has been investigated by means of DFT calculations at the M06/def-TZVP//B97D3/def2-TZVP level of theory, in combination with the SMD solvation method. The reaction rate is determined by the formation of the coordinatively unsaturated doublet-state Fe(CO)(3)(P) precursor followed by the diazoalkane coordination and the N-2 extrusion. The free energy of activation is predicted to be 18.5 and 28.2 kcal/mol for the PF3 and PPh3 containing systems, respectively. Thus, in the presence of less basic P-donor ligands with stronger pi-acceptor properties, a significant increase in the reaction rate can be expected. According to energy decomposition analysis combined with natural orbitals of chemical valence (EDA-NOCV) calculations, diazomethane in the Fe(CO)(3)(phosphine)(eta(1)-CH2N2) adduct reveals a pi-donor-pi-acceptor type of coordination.

引用

页数：13

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