Catalytic Carbodiimide Guanylation by a Nucleophilic, High Spin Iron(II) Imido Complex
- 1 April 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (14), 5324-5329
- https://doi.org/10.1021/jacs.1c02068
Abstract
Reduction of the three-coordinate iron(III) imido [Ph2B(tBuIm)2Fe═NDipp] (1) affords [Ph2B(tBuIm)2Fe═NDipp][K(18-C-6)THF2] (2), a rare example of a high-spin (S = 2) iron(II) imido complex. Unusually for a late metal imido complex, the imido ligand in 2 has nucleophilic character, as demonstrated by the reaction with DippNH2, which establishes an equilibrium with the bis(anilido) complex [Ph2B(tBuIm)2Fe(NHDipp)2][K(18-C-6)THF2] (3). In an unusual transformation, formal insertion of iPrN═C═NiPr into the Fe═N(imido) bond yields the guanidinate [Ph2B(tBuIm)2Fe(iPrN)2CNDipp][K(18-C-6)THF2] (4). Reaction of 4 with excess DippNH2 provides 3, along with the guanidine (iPrNH)2C═NDipp. As suggested by these stoichiometric reactions, 2 is an efficient catalyst for the guanylation of carbodiimides, converting a wide range of aniline substrates under mild conditions.Funding Information
- Basic Energy Sciences (DE-SC0019466)
This publication has 56 references indexed in Scilit:
- Two-State Reactivity in Iron-Catalyzed Alkene Isomerization Confers σ-Base ResistanceJournal of the American Chemical Society, 2020
- Reactivity of terminal imido complexes of group 4–6 metals: Stoichiometric and catalytic reactions involving cycloaddition with unsaturated organic moleculesCoordination Chemistry Reviews, 2020
- Catalytic formal [2+2+1] synthesis of pyrroles from alkynes and diazenes via TiII/TiIV redox catalysisNature Chemistry, 2015
- Designing Catalysts for Nitrene Transfer Using Early Transition Metals and Redox-Active LigandsInorganic Chemistry, 2011
- One-Step Route to 2,3-Diaminopyrroles Using a Titanium-Catalyzed Four-Component CouplingOrganometallics, 2009
- Oxidatively Induced Abstraction Reactions. A Synthetic Approach to Low-Coordinate and Reactive Early Transition Metal Complexes Containing Metal−Ligand Multiple BondsAccounts of Chemical Research, 2006
- Ti(NMe2)4 and [HNMe2Ph][B(C6F5)4]: A Convenient Blend for Effective Catalytic Carboamination of AlkynesOrganometallics, 2006
- Carboamination: Additions of Imine CN Bonds Across Alkynes Catalyzed by Imidozirconium ComplexesAngewandte Chemie, 2004
- Pyrrole Syntheses Based on Titanium-Catalyzed Hydroamination of DiynesOrganic Letters, 2004
- Imidotitanium Complexes as Hydroamination Catalysts: Substantially Enhanced Reactivity from an Unexpected Cyclopentadienide/Amide Ligand ExchangeJournal of the American Chemical Society, 2001