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Transition metal azide complex

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Transition metal azide complexes are coordination complexes containing one or more azide (N3−) ligands.[2]

Azide is a common ligand in coordination chemistry. The structure of [Co(ethylenediamine)2(SO3)N3].[1]

Structure and bonding

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Azide is a pseudohalide but more nucleophilic than chloride. As a monodentate ligand, azide binds through one of the two terminal nitrogen atoms, i.e. M-N=N=N. The N3 unit is linear or nearly so. The M-N-N angles are quite bent. Azide functions as a bridging ligand via two bonding modes. Commonly the metals share the same nitrogen ("N-diazonium" mode). Less common is the motif M-N=N=N-M, illustrated by [Cu(N3)(PPh3)2]2.[2]

Homoleptic complexes

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Structure of [Fe2(N3)10]4-.[3]
 
Structure of [Nb(N3)7]2-.[4]-
See also: Homoleptic azido compounds

Many homoleptic complexes (with only one kind of ligand) are known. Coordination numbers range from 2 (e.g., [Au(N3)2]−) to 7 (e.g., [W(N3)7]−). Many homoleptic complexes are octahedral anions of the type [M(N3)6]n-:

  • dianions for tetravalent metals V, Pt, Ti, Zr, Hf
  • trianions for trivalent metals Cr, Fe, Ru, Rh, Ir
  • tetraanions for the divalent Ni

For some metals, homoleptic complexes exist in two oxidation states: [Au(N3)2]− vs [Au(N3)4]− and [Pt(N3)6]4- vs [Pt(N3)4]2-.[2]

Mixed ligand complexes

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Structure of trans-PdN3(CH3)(PMe3)2. Distances are in picometers.[5]

Azide forms myriad mixed ligand complexes. Examples include Zn(N3)2(NH3)2 and (C5H5)2Ti(N3)2.

Synthesis and reactions

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Traditionally, metal azide complexes are prepared by salt metathesis, e.g. the reaction of metal chlorides with sodium azide. In some cases, trimethylsilyl azide is employed as the azide source.

Heating and, in some cases, UV radiation often cause azide complexes to release nitrogen gas. This behavior is the basis of their frequent explosive properties (see lead azide). With suitable coligands, the resulting metal nitrido complex can be isolated.

Azide ligands are react with nitrosonium to give nitrous oxide. This reaction is used to generate coordinatively unsaturated complexes.[6]

[Co(NH3)5N3]2+ + NO+ + H2O → [Co(NH3)5(H2O)]3+ + N2O + N2

This approach was used to prepare the previously elusive dicationic complex pentamminecobalt(III) perchlorate, [Co(NH3)5(OClO3)]2+.[7]

References

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  1. ^ I. Bernal; J. Cetrullo; W. G. Jackson (1993). "The Phenomenon of Conglomerate Crystallization in Coordination Compounds. XXIII: The Crystallization Behavior of [cis-Co(en)2(N3)(SO3)]·2H2O (I) and of [cis-Co(en)2(NO2)(SO3)]·H2O (II)". Struct. Chem. 4: 235. doi:10.1007/BF00673698. S2CID 94847897.
  2. ^ a b c Fehlhammer, Wolf Peter; Beck, Wolfgang (2013). "Azide Chemistry - an Inorganic Perspective, Part I Metal Azides: Overview, General Trends and Recent Developments". Zeitschrift für Anorganische und Allgemeine Chemie. 639 (7): 1053–1082. doi:10.1002/zaac.201300162.
  3. ^ De Munno, Giovanni; Poerio, Teresa; Viau, Guillaume; Julve, Miguel; Lloret, Francesc (1997). "Ferromagnetic Coupling in the Bis(μ-end-on-azido)iron(III) Dinuclear Complex Anion of[FeII(bpym)3]2[Fe2III(N3)10]·2H2O". Angewandte Chemie International Edition in English. 36 (1314): 1459–1461. doi:10.1002/anie.199714591.
  4. ^ Haiges, Ralf; Boatz, Jerry A.; Yousufuddin, Muhammed; Christe, Karl O. (2007). "Monocapped Trigonal-Prismatic Transition-Metal Heptaazides: Syntheses, Properties, and Structures of [Nb(N3)7]2− and [Ta(N3)7]2−". Angewandte Chemie International Edition. 46 (16): 2869–2874. doi:10.1002/anie.200604520. PMID 17348060.
  5. ^ Kim, Yong-Joo; Kim, Dae-Hun; Lee, Jae-Young; Lee, Soon-W. (1997). "Preparation and Reactions of Methylpalladium(II) and -Platinum(II) Azido Complexes. The Crystal Structure of trans-PdMe(N3)(PMe3)2 and trans-PdMe[CN4(C6H11)](PMe3)2". Journal of Organometallic Chemistry. 538 (1–2): 189–197. doi:10.1016/S0022-328X(96)06908-2.
  6. ^ Buckingham, David A.; Olsen, I. I.; Sargeson, Alan M.; Satrapa, H. (1967). "The Mechanism of Substitution Reactions of Pentamminecobalt(III) Complexes. Product Distributions in the Induced Aquation of Some [Co(NH3)5X]2+ Ions in the Presence of Added Anions". Inorganic Chemistry. 6 (5): 1027–1032. doi:10.1021/ic50051a038.
  7. ^ Harrowfield, J. Macb.; Sargeson, A. M.; Singh, B.; Sullivan, J. C. (1975). "Trapping of Labile Cobalt(III) Complexes. Characterization of the Perchloratopentaamminecobalt(III) Ion". Inorganic Chemistry. 14 (11): 2864–2865. doi:10.1021/ic50153a059.
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