PMID- 32926539
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20231110
IS  - 1521-3773 (Electronic)
IS  - 1433-7851 (Print)
IS  - 1433-7851 (Linking)
VI  - 59
IP  - 51
DP  - 2020 Dec 14
TI  - Closed Shell Iron(IV) Oxo Complex with an Fe-O Triple Bond: Computational Design, 
      Synthesis, and Reactivity.
PG  - 23137-23144
LID - 10.1002/anie.202009347 [doi]
AB  - Iron(IV)-oxo intermediates in nature contain two unpaired electrons in the Fe-O 
      antibonding orbitals, which are thought to contribute to their high reactivity. 
      To challenge this hypothesis, we designed and synthesized closed-shell singlet 
      iron(IV) oxo complex [(quinisox)Fe(O)](+) (1(+) ; 
      quinisox-H=(N-(2-(2-isoxazoline-3-yl)phenyl)quinoline-8-carboxamide). We 
      identified the quinisox ligand by DFT computational screening out of over 
      450 candidates. After the ligand synthesis, we detected 1(+) in the gas phase and 
      confirmed its spin state by visible and infrared photodissociation spectroscopy 
      (IRPD). The Fe-O stretching frequency in 1(+) is 960.5 cm(-1) , consistent with 
      an Fe-O triple bond, which was also confirmed by multireference calculations. The 
      unprecedented bond strength is accompanied by high gas-phase reactivity of 1(+) 
      in oxygen atom transfer (OAT) and in proton-coupled electron transfer reactions. 
      This challenges the current view of the spin-state driven reactivity of the Fe-O 
      complexes.
CI  - (c) 2020 The Authors. Published by Wiley-VCH GmbH.
FAU - Andris, Erik
AU  - Andris E
AUID- ORCID: 0000-0002-9336-0157
AD  - Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 
      6525 AJ, Nijmegen, The Netherlands.
AD  - Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, 
      Flemingovo namesti 2, 16610, Praha 6, Czech Republic.
FAU - Segers, Koen
AU  - Segers K
AD  - Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 
      6525 AJ, Nijmegen, The Netherlands.
FAU - Mehara, Jaya
AU  - Mehara J
AUID- ORCID: 0000-0003-1959-3478
AD  - Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 
      6525 AJ, Nijmegen, The Netherlands.
FAU - Rulisek, Lubomir
AU  - Rulisek L
AUID- ORCID: 0000-0002-7769-7059
AD  - Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, 
      Flemingovo namesti 2, 16610, Praha 6, Czech Republic.
FAU - Roithova, Jana
AU  - Roithova J
AUID- ORCID: 0000-0001-5144-0688
AD  - Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 
      6525 AJ, Nijmegen, The Netherlands.
LA  - eng
GR  - CoG No. 682275/H2020 European Research Council/
GR  - LTAUSA19148/Ministerstvo Skolstvi, Mladeze a Telovychovy/
PT  - Journal Article
DEP - 20201029
PL  - Germany
TA  - Angew Chem Int Ed Engl
JT  - Angewandte Chemie (International ed. in English)
JID - 0370543
SB  - IM
PMC - PMC7756500
OTO - NOTNLM
OT  - ion spectroscopy
OT  - iron oxo complexes
OT  - ligand design
OT  - spin state
COIS- The authors declare no conflict of interest.
EDAT- 2020/09/15 06:00
MHDA- 2020/09/15 06:01
PMCR- 2020/12/23
CRDT- 2020/09/14 15:51
PHST- 2020/07/07 00:00 [received]
PHST- 2020/09/15 06:00 [pubmed]
PHST- 2020/09/15 06:01 [medline]
PHST- 2020/09/14 15:51 [entrez]
PHST- 2020/12/23 00:00 [pmc-release]
AID - ANIE202009347 [pii]
AID - 10.1002/anie.202009347 [doi]
PST - ppublish
SO  - Angew Chem Int Ed Engl. 2020 Dec 14;59(51):23137-23144. doi: 
      10.1002/anie.202009347. Epub 2020 Oct 29.