Literature DB >> 30974012

Unprecedented Five-Coordinate Iron(IV) Imides Generate Divergent Spin States Based on the Imide R-Groups.

Markus R Anneser1, Gaya R Elpitiya1, Jacob Townsend1, Elizabeth J Johnson2, Xian B Powers1, Joseph F DeJesus1, Konstantinos D Vogiatzis1, David M Jenkins1.   

Abstract

Three five-coordinate iron(IV) imide complexes have been synthen class="Chemical">sized and characterized. These novel structures have disparate spin states on the iron as a function of the R-group attached to the imide, with alkyl groups leading to low-spin diamagnetic (S=0) complexes and an aryl group leading to an intermediate-spin (S=1) complex. The different spin states lead to significant differences in the bonding about the iron center as well as the spectroscopic properties of these complexes. Mössbauer spectroscopy confirmed that all three imide complexes are in the iron(IV) oxidation state. The combination of diamagnetism and 15 N labeling allowed for the first 15 N NMR resonance recorded on an iron imide. Multi-reference calculations corroborate the experimental structural findings and suggest how the bonding is distinctly different on the imide ligand between the two spin states.
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Entities:  

Keywords:  N-heterocyclic carbenes; imides; iron; macrocycles; organometallic chemistry

Year:  2019        PMID: 30974012      PMCID: PMC6546507          DOI: 10.1002/anie.201903132

Source DB:  PubMed          Journal:  Angew Chem Int Ed Engl        ISSN: 1433-7851            Impact factor:   15.336


  31 in total

1.  Synthesis and hydrogenation of bis(imino)pyridine iron imides.

Authors:  Suzanne C Bart; Emil Lobkovsky; Eckhard Bill; Paul J Chirik
Journal:  J Am Chem Soc       Date:  2006-04-26       Impact factor: 15.419

2.  Characterization of the terminal iron(IV) imides [[PhBP(t)(Bu)2(pz')]Fe(IV)NAd]+.

Authors:  Christine M Thomas; Neal P Mankad; Jonas C Peters
Journal:  J Am Chem Soc       Date:  2006-04-19       Impact factor: 15.419

3.  A tosylimido analogue of a nonheme oxoiron(IV) complex.

Authors:  Eric J Klinker; Timothy A Jackson; Michael P Jensen; Audria Stubna; Gergely Juhász; Emile L Bominaar; Eckard Münck; Lawrence Que
Journal:  Angew Chem Int Ed Engl       Date:  2006-11-13       Impact factor: 15.336

4.  Vibrational spectroscopy and analysis of pseudo-tetrahedral complexes with metal imido bonds.

Authors:  Mark P Mehn; Steven D Brown; David M Jenkins; Jonas C Peters; Lawrence Que
Journal:  Inorg Chem       Date:  2006-09-04       Impact factor: 5.165

5.  Fe(I)-mediated reductive cleavage and coupling of CO(2): an Fe(II)(mu-O, mu-CO)Fe(II) core.

Authors:  Connie C Lu; Caroline T Saouma; Michael W Day; Jonas C Peters
Journal:  J Am Chem Soc       Date:  2007-01-10       Impact factor: 15.419

6.  Ground-state singlet L3Fe-(mu-N)-FeL3 and L3Fe(NR) complexes featuring pseudotetrahedral Fe(II) centers.

Authors:  Steven D Brown; Jonas C Peters
Journal:  J Am Chem Soc       Date:  2005-02-16       Impact factor: 15.419

7.  A tetrahedrally coordinated L3Fe-Nx platform that accommodates terminal nitride (Fe(IV)N) and dinitrogen (Fe(I)-N2-Fe(I)) ligands.

Authors:  Theodore A Betley; Jonas C Peters
Journal:  J Am Chem Soc       Date:  2004-05-26       Impact factor: 15.419

8.  A low-spin d5 iron imide: nitrene capture by low-coordinate iron(I) provides the 4-coordinate Fe(III) complex [PhB(CH2PPh2)3]Fe=N-p-tolyl.

Authors:  Steven D Brown; Theodore A Betley; Jonas C Peters
Journal:  J Am Chem Soc       Date:  2003-01-15       Impact factor: 15.419

Review 9.  Mid- to high-valent imido and nitrido complexes of iron.

Authors:  Mark P Mehn; Jonas C Peters
Journal:  J Inorg Biochem       Date:  2006-03-10       Impact factor: 4.155

10.  Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms.

Authors:  Theodore A Betley; Jonas C Peters
Journal:  J Am Chem Soc       Date:  2003-09-10       Impact factor: 15.419

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  8 in total

1.  Direct Manipulation of Metal Imido Geometry: Key Principles to Enhance C-H Amination Efficacy.

Authors:  Yunjung Baek; Elisabeth T Hennessy; Theodore A Betley
Journal:  J Am Chem Soc       Date:  2019-10-10       Impact factor: 15.419

2.  Elucidation of the Reaction Mechanism of C2 + N1 Aziridination from Tetracarbene Iron Catalysts.

Authors:  Sara B Isbill; Preeti P Chandrachud; Jesse L Kern; David M Jenkins; Sharani Roy
Journal:  ACS Catal       Date:  2019-05-31       Impact factor: 13.084

3.  Reversible C-C Bond Cleavage of a Cobalt Diketimide into an Elusive Cobalt Aryl Nitrenoid Complex.

Authors:  Yunjung Baek; Theodore A Betley
Journal:  Angew Chem Int Ed Engl       Date:  2022-03-02       Impact factor: 15.336

4.  Between imide, imidyl and nitrene - an imido iron complex in two oxidation states.

Authors:  Sascha Reith; Serhiy Demeshko; Beatrice Battistella; Alexander Reckziegel; Christian Schneider; Andreas Stoy; Crispin Lichtenberg; Franc Meyer; Dominik Munz; C Gunnar Werncke
Journal:  Chem Sci       Date:  2022-06-09       Impact factor: 9.969

5.  A Chiral Macrocyclic Tetra-N-Heterocyclic Carbene Yields an "All Carbene" Iron Alkylidene Complex.

Authors:  Joseph F DeJesus; David M Jenkins
Journal:  Chemistry       Date:  2020-01-22       Impact factor: 5.236

Review 6.  A μ-Phosphido Diiron Dumbbell in Multiple Oxidation States.

Authors:  Munmun Ghosh; Hanna H Cramer; Sebastian Dechert; Serhiy Demeshko; Michael John; Max M Hansmann; Shengfa Ye; Franc Meyer
Journal:  Angew Chem Int Ed Engl       Date:  2019-08-23       Impact factor: 15.336

7.  Stabilization of a high-spin three-coordinate Fe(iii) imidyl complex by radical delocalization.

Authors:  Po-Chun Yang; Kuan-Po Yu; Chi-Tien Hsieh; Junjie Zou; Chia-Te Fang; Hsin-Kuan Liu; Chih-Wen Pao; Liang Deng; Mu-Jeng Cheng; Chun-Yi Lin
Journal:  Chem Sci       Date:  2022-07-21       Impact factor: 9.969

8.  Umpolung in a Pair of Cobalt(III) Terminal Imido/Imidyl Complexes.

Authors:  Weiqing Mao; Dominik Fehn; Frank W Heinemann; Andreas Scheurer; Maurice van Gastel; Sergio A V Jannuzzi; Serena DeBeer; Dominik Munz; Karsten Meyer
Journal:  Angew Chem Int Ed Engl       Date:  2022-08-03       Impact factor: 16.823

  8 in total

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