Closed-shell and Open-shell Square-planar Iridium Nitrido Complexes

Overview

Journal Nat Chem

Specialty Chemistry

Date 2012 Jun 22

PMID 22717440

Citations 32

Authors

Markus G Scheibel

Bjorn Askevold

Frank W Heinemann

Edward J Reijerse

Bas de Bruin

Sven Schneider

Affiliations

Soon will be listed here.

Abstract

Coupling reactions of nitrogen atoms represent elementary steps to many important heterogeneously catalysed reactions, such as the Haber-Bosch process or the selective catalytic reduction of NO(x) to give N(2). For molecular nitrido (and related oxo) complexes, it is well established that the intrinsic reactivity, for example nucleophilicity or electrophilicity of the nitrido (or oxo) ligand, can be attributed to M-N (M-O) ground-state bonding. In recent years, nitrogen (oxygen)-centred radical reactivity was ascribed to the possible redox non-innocence of nitrido (oxo) ligands. However, unequivocal spectroscopic characterization of such transient nitridyl {M=N(•)} (or oxyl {M-O(•)}) complexes remained elusive. Here we describe the synthesis and characterization of the novel, closed-shell and open-shell square-planar iridium nitrido complexes [IrN(L(t-Bu))](+) and [IrN(L(t-Bu))] (L(t-Bu)=N(CHCHP-t-Bu(2))(2)). Spectroscopic characterization and quantum chemical calculations for [IrN(L(t-Bu))] indicate a considerable nitridyl, {Ir=N(•)}, radical character. The clean formation of Ir(I)-N(2) complexes via binuclear coupling is rationalized in terms of nitrido redox non-innocence in [IrN(L(t-Bu))].

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References

Sieh D, Schoffel J, Burger P . Synthesis of a chloro protected iridium nitrido complex. Dalton Trans. 2011; 40(37):9512-24. DOI: 10.1039/c1dt10886g. View

Bonomo L, Solari E, Scopelliti R, Floriani C . Ruthenium Nitrides: Redox Chemistry and Photolability of the Ru-Nitrido Group This work was supported by the "Fonds National Suisse de la Recherche Scientifique" (Grant No. 20-61'246.00). . Angew Chem Int Ed Engl. 2001; 40(13):2529-2531. View

Berry J, Bill E, Bothe E, Debeer George S, Mienert B, Neese F . An octahedral coordination complex of iron(VI). Science. 2006; 312(5782):1937-41. DOI: 10.1126/science.1128506. View

Thomson R, Cantat T, Scott B, Morris D, Batista E, Kiplinger J . Uranium azide photolysis results in C-H bond activation and provides evidence for a terminal uranium nitride. Nat Chem. 2010; 2(9):723-9. DOI: 10.1038/nchem.705. View

Schlangen M, Schwarz H . Ligand and electronic-structure effects in metal-mediated gas-phase activation of methane: a cold approach to a hot problem. Dalton Trans. 2009; (46):10155-65. DOI: 10.1039/b915165f. View

Bendix J, Anthon C, Schau-Magnussen M, Brock-Nannestad T, Vibenholt J, Rehman M . Heterobimetallic nitride complexes from terminal chromium(V) nitride complexes: hyperfine coupling increases with distance. Angew Chem Int Ed Engl. 2011; 50(19):4480-3. DOI: 10.1002/anie.201008153. View

Miyazato Y, Wada T, Muckerman J, Fujita E, Tanaka K . Generation of a RuII-semiquinone-anilino-radical complex through the deprotonation of a RuIII-semiquinone-anilido complex. Angew Chem Int Ed Engl. 2007; 46(30):5728-30. DOI: 10.1002/anie.200701600. View

Ueta H, Gleeson M, Kleyn A . Scattering of hyperthermal nitrogen atoms from the Ag(111) surface. J Phys Chem A. 2009; 113(52):15092-9. DOI: 10.1021/jp905167p. View

Mankad N, Antholine W, Szilagyi R, Peters J . Three-coordinate copper(I) amido and aminyl radical complexes. J Am Chem Soc. 2009; 131(11):3878-80. PMC: 3110787. DOI: 10.1021/ja809834k. View

10.

Tran B, Washington M, Henckel D, Gao X, Park H, Pink M . A four coordinate parent imide via a titanium nitridyl. Chem Commun (Camb). 2011; 48(10):1529-31. DOI: 10.1039/c1cc14574f. View

11.

Atienza C, Bowman A, Lobkovsky E, Chirik P . Photolysis and thermolysis of bis(imino)pyridine cobalt azides: C-H activation from putative cobalt nitrido complexes. J Am Chem Soc. 2010; 132(46):16343-5. DOI: 10.1021/ja107288x. View

12.

Ertl G . Reactions at surfaces: from atoms to complexity (Nobel Lecture). Angew Chem Int Ed Engl. 2008; 47(19):3524-35. DOI: 10.1002/anie.200800480. View

13.

Ye S, Neese F . Nonheme oxo-iron(IV) intermediates form an oxyl radical upon approaching the C-H bond activation transition state. Proc Natl Acad Sci U S A. 2011; 108(4):1228-33. PMC: 3029731. DOI: 10.1073/pnas.1008411108. View

14.

Eckert N, Vaddadi S, Stoian S, Lachicotte R, Cundari T, Holland P . Coordination-number dependence of reactivity in an imidoiron(III) complex. Angew Chem Int Ed Engl. 2006; 45(41):6868-71. DOI: 10.1002/anie.200601927. View

15.

Scepaniak J, Young J, Bontchev R, Smith J . Formation of ammonia from an iron nitrido complex. Angew Chem Int Ed Engl. 2009; 48(17):3158-60. DOI: 10.1002/anie.200900381. View

16.

Walstrom A, Pink M, Yang X, Tomaszewski J, Baik M, Caulton K . A facile approach to a d4 RuN: moiety. J Am Chem Soc. 2005; 127(15):5330-1. DOI: 10.1021/ja050361k. View

17.

King E, Hennessy E, Betley T . Catalytic C-H bond amination from high-spin iron imido complexes. J Am Chem Soc. 2011; 133(13):4917-23. DOI: 10.1021/ja110066j. View

18.

Betley T, Peters J . A tetrahedrally coordinated L3Fe-Nx platform that accommodates terminal nitride (Fe(IV)N) and dinitrogen (Fe(I)-N2-Fe(I)) ligands. J Am Chem Soc. 2004; 126(20):6252-4. DOI: 10.1021/ja048713v. View

19.

Askevold B, Nieto J, Tussupbayev S, Diefenbach M, Herdtweck E, Holthausen M . Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand. Nat Chem. 2011; 3(7):532-7. DOI: 10.1038/nchem.1051. View

20.

Seymore S, Brown S . Polar effects in nitride coupling reactions. Inorg Chem. 2002; 41(3):462-9. DOI: 10.1021/ic010844z. View