Element-Element Bond Formation Upon Oxidation and Reduction

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2020 Feb 5

PMID 32017349

Citations 5

Authors

Martin Piesch

Christian Grassl

Manfred Scheer

Affiliations

Soon will be listed here.

Abstract

The redox chemistry of [(Cp'''Co) (μ,η :η -E ) ] (E=P (1), As (2); Cp'''=1,2,4-tri(tert-butyl)cyclopentadienyl) was investigated. Both compounds can be oxidized and reduced twice. That way, the monocations [(Cp'''Co) (μ,η :η -E )][X] (E=P, X=BF (3 a), [FAl] (3 b); E=As, X=BF (4 a), [FAl] (4 b)), the dications [(Cp'''Co) (μ,η :η -E )][TEF] (E=P (5), As (6)), and the monoanions [K(18-c-6)(dme) ][(Cp'''Co) (μ,η :η -E )] (E=P (7), As (8)) were isolated. Further reduction of 7 leads to the dianionic complex [K(18-c-6)(dme) ][K(18-c-6)][(Cp'''Co) (μ,η :η -P )] (9), in which the cyclo-P ligand has rearranged to a chain-like P ligand. Further reduction of 8 can be achieved with an excess of potassium under the formation of [K(dme) ][(Cp'''Co) (μ,η :η -As )] (10) and the elimination of an As unit. Compound 10 represents the first example of an allylic As ligand incorporated into a triple-decker complex.

Citing Articles

Transition-Metal-Stabilized Heavy Tetraphospholide Anions.

Kelly J, Streitferdt V, Dimitrova M, Westermair F, Gschwind R, Berger R J Am Chem Soc. 2022; 144(44):20434-20441.

PMID: 36315515 PMC: 9650697. DOI: 10.1021/jacs.2c08754.

Halogenation and Nucleophilic Quenching: Two Routes to E-X Bond Formation in Cobalt Triple-Decker Complexes (E=As, P; X=F, Cl, Br, I).

Garbagnati A, Piesch M, Seidl M, Balazs G, Scheer M Chemistry. 2022; 28(43):e202201026.

PMID: 35575044 PMC: 9400891. DOI: 10.1002/chem.202201026.

E Transfer (E=P, As) to Ni Complexes.

Heinl V, Schmidt M, Eckhardt M, Eberl M, Seitz A, Balazs G Chemistry. 2021; 27(45):11649-11655.

PMID: 33971062 PMC: 8453863. DOI: 10.1002/chem.202101119.

Redox Chemistry of Heterobimetallic Polypnictogen Triple-Decker Complexes - Rearrangement, Fragmentation and Transfer.

Piesch M, Reichl S, Riesinger C, Seidl M, Balazs G, Scheer M Chemistry. 2021; 27(35):9129-9140.

PMID: 33857335 PMC: 8360055. DOI: 10.1002/chem.202100844.

Element-Element Bond Formation upon Oxidation and Reduction.

Piesch M, Grassl C, Scheer M Angew Chem Int Ed Engl. 2020; 59(18):7154-7160.

PMID: 32017349 PMC: 7216884. DOI: 10.1002/anie.201916622.

References

Alvarez S . A cartography of the van der Waals territories. Dalton Trans. 2013; 42(24):8617-36. DOI: 10.1039/c3dt50599e. View

Schoo C, Koppe R, Piesch M, Gamer M, Konchenko S, Scheer M . Open Chain Polyarsenides of the Lanthanides. Chemistry. 2018; 24(31):7890-7895. DOI: 10.1002/chem.201800539. View

Fleischmann M, Dielmann F, Balazs G, Scheer M . Oxidation Chemistry of Inorganic Benzene Complexes. Chemistry. 2016; 22(43):15248-15251. DOI: 10.1002/chem.201603530. View

Dielmann F, Timoshkin A, Piesch M, Balazs G, Scheer M . The Cobalt cyclo-P Sandwich Complex and Its Role in the Formation of Polyphosphorus Compounds. Angew Chem Int Ed Engl. 2017; 56(6):1671-1675. PMC: 5299486. DOI: 10.1002/anie.201610967. View

Grassl C, Bodensteiner M, Zabel M, Scheer M . Synthesis of arsenic-rich As ligand complexes from yellow arsenic. Chem Sci. 2018; 6(2):1379-1382. PMC: 5811125. DOI: 10.1039/c4sc03543g. View

Piesch M, Grassl C, Scheer M . Element-Element Bond Formation upon Oxidation and Reduction. Angew Chem Int Ed Engl. 2020; 59(18):7154-7160. PMC: 7216884. DOI: 10.1002/anie.201916622. View

Butovskiy M, Balazs G, Bodensteiner M, Peresypkina E, Virovets A, Sutter J . Ferrocene and pentaphosphaferrocene: a comparative study regarding redox chemistry. Angew Chem Int Ed Engl. 2013; 52(10):2972-6. DOI: 10.1002/anie.201209329. View

Schmidt M, Konieczny D, Peresypkina E, Virovets A, Balazs G, Bodensteiner M . Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments. Angew Chem Int Ed Engl. 2017; 56(25):7307-7311. DOI: 10.1002/anie.201702903. View

Connelly N, Geiger W . Chemical Redox Agents for Organometallic Chemistry. Chem Rev. 1996; 96(2):877-910. DOI: 10.1021/cr940053x. View

10.

Piesch M, Dielmann F, Reichl S, Scheer M . A General Pathway to Heterobimetallic Triple-Decker Complexes. Chemistry. 2019; 26(7):1518-1524. PMC: 7028134. DOI: 10.1002/chem.201905240. View

11.

Pyykko P, Atsumi M . Molecular double-bond covalent radii for elements Li-E112. Chemistry. 2009; 15(46):12770-9. DOI: 10.1002/chem.200901472. View

12.

Cataldo L, Choua S, Berclaz T, Geoffroy M, Mezailles N, Ricard L . Formation of a phosphorus-phosphorus bond by successive one-electron reductions of a two-phosphinines-containing macrocycle: crystal structures, EPR, and DFT investigations. J Am Chem Soc. 2001; 123(27):6654-61. DOI: 10.1021/ja010331r. View

13.

Dutsch L, Fleischmann M, Welsch S, Balazs G, Kremer W, Scheer M . Dicationic E Chains (E=P, As, Sb, Bi) Embedded in the Coordination Sphere of Transition Metals. Angew Chem Int Ed Engl. 2018; 57(12):3256-3261. DOI: 10.1002/anie.201712884. View

14.

Kochner T, Engesser T, Scherer H, Plattner D, Steffani A, Krossing I . [P9]+ [Al(OR(F))4)]-, the salt of a homopolyatomic phosphorus cation. Angew Chem Int Ed Engl. 2012; 51(26):6529-31. DOI: 10.1002/anie.201201262. View

15.

Moret M, Zhang L, Peters J . A polar copper-boron one-electron σ-bond. J Am Chem Soc. 2013; 135(10):3792-5. DOI: 10.1021/ja4006578. View

16.

Madl E, Balazs G, Peresypkina E, Scheer M . Unexpected Reactivity of [(η(5) -1,2,4-tBu3 C5 H2 )Ni(η(3) -P3 )] towards Main Group Nucleophiles and by Reduction. Angew Chem Int Ed Engl. 2016; 55(27):7702-7. DOI: 10.1002/anie.201601775. View

17.

Li T, Arleth N, Gamer M, Koppe R, Augenstein T, Dielmann F . Intramolecular phosphorus-phosphorus bond formation within a Co2P4 core. Inorg Chem. 2013; 52(24):14231-6. DOI: 10.1021/ic402159y. View

18.

Dielmann F, Sierka M, Virovets A, Scheer M . Access to extended polyphosphorus frameworks. Angew Chem Int Ed Engl. 2010; 49(38):6860-4. DOI: 10.1002/anie.201001000. View

19.

Canac , Bourissou , Baceiredo , Gornitzka , Schoeller , BERTRAND . Isolation of a benzene valence isomer with one-electron phosphorus-phosphorus bonds . Science. 1998; 279(5359):2080-2. DOI: 10.1126/science.279.5359.2080. View

20.

Pyykko P, Atsumi M . Molecular single-bond covalent radii for elements 1-118. Chemistry. 2008; 15(1):186-97. DOI: 10.1002/chem.200800987. View