Dataset Information

Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex.

ABSTRACT: Earth-abundant metal pincer complexes have played an important role in homogeneous catalysis during the last ten years. Yet, despite intense research efforts, the synthesis of iron PCcarbeneP pincer complexes has so far remained elusive. Here we report the synthesis of the first PCNHCP functionalized iron complex [(PCNHCP)FeCl2] (1) and the reactivity of the corresponding trans-dihydride iron(II) dinitrogen complex [(PCNHCP)Fe(H)2N2)] (2). Complex 2 is stable under an atmosphere of N2 and is highly active for hydrogen isotope exchange at (hetero)aromatic hydrocarbons under mild conditions (50 °C, N2). With benzene-d6 as the deuterium source, easily reducible functional groups such as esters and amides are well tolerated, contributing to the overall wide substrate scope (e.g., halides, ethers, and amines). DFT studies suggest a complex assisted ?-bond metathesis pathway for C(sp2)-H bond activation, which is further discussed in this study.

SUBMITTER: Garhwal S

PROVIDER: S-EPMC7586338 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex.

Garhwal Subhash S Kaushansky Alexander A Fridman Natalia N Shimon Linda J W LJW Ruiter Graham de G

Journal of the American Chemical Society 20200922 40

Earth-abundant metal pincer complexes have played an important role in homogeneous catalysis during the last ten years. Yet, despite intense research efforts, the synthesis of iron PCcarbeneP pincer complexes has so far remained elusive. Here we report the synthesis of the first PCNHCP functionalized iron complex [(PCNHCP)FeCl2] (1) and the reactivity of the corresponding trans-dihydride iron(II) dinitrogen complex [(PCNHCP)Fe( ...[more]

PMID: 32902969

Similar Datasets

Project description:Recently, the NHC?B 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 B?NHC molecule 1 has been published in Science where it is described as a stabilized B2 molecule in its 1? excited state (B2*) (NHC = N-heterocyclic carbene C3N2H2(C6H3Pri2-2,6)2). The bonding of 1 based on sophisticated calculations and the BB distances of the solid compound was discussed as the first example of a B2 triple bond in a stable molecule. Now we present an only experimentally based interpretation of 1via detailed thermodynamic considerations, including its fragmentation to B2 molecules. Furthermore, from the vibrational spectrum force constants (fBB for the BB bond and fBC for the BC bond) were extracted, which are classical examples to indicate single, double and triple CC bonds in organic chemistry. The consequence of both properties of 1 (?E and f) generates a new interpretation which is in contrast to the triple bond donor-acceptor description visualized by arrows and which casts a critical light on the interpretation of any NHC "stabilized" molecule.

Dataset Information

Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex.

Publications

Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets