Transition Metal Complexes with Organoazide Ligands: Synthesis, Structural Chemistry, and Reactivity

Barz, Michael; Herdtweck, Eberhardt; Thiel, Werner R.

doi:10.1002/(sici)1521-3773(19980904)37:16<2262::aid-anie2262>3.0.co;2-x

Cited by 79 publications

(24 citation statements)

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“…The scarce literature on organic azides does provide diverse evidence on ligand behavioráinásolutioná [32][33][34].áTheáfirstátwoástudiesáreport on a monodentate azide ligand being the terminal nitrogen of the azido group coordinated to the metal. The complex suffers loss of N 2 leading, by rearrangement and via an intermediate, to an imido complex.…”

Section: Esi-msástudiesáofácu(ii)-ureaácomplexáformationáalso Reportementioning

confidence: 99%

“…In agreement with experimental information on azide-metalácomplexesá [32][33][34],átheápresentátheoretical calculations support the view that although bidentate complexes are energetically more stable, monodentate structures can also be observed in mono positively charged complexes involving 3-azidopropionitrile and Ni. The specific structure of these complexes should reflect the fact that in comparison with metal-ligand interactions, ligand-ligand interactions are significantly weaker.…”

Section: Theoretical Studymentioning

confidence: 99%

“…Although the formation of complexes involving organic azides and transition metals hasábeenápreviouslyáinvestigatedá [32][33][34],átheácoordina-tion site and coordination number are still matters of debate and deserve further attention. The work reportedáináreferencesá [32,á33]áshowedáthatátheáligands, phenyl, and substituted phenyl azides, coordinate metal centers only by the terminal nitrogen of the azido group.…”

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confidence: 99%

“…In both cases, upon molecular nitrogen extrusion, the metal is coordinated by the alkylated nitrogen. However, when another functional group is present besidesátheáazidoágroupá [34],átheácomplexáseemsátoábe bidentate. In this case it is observed that the azido group coordinates by the alkylated nitrogen of the azido group.…”

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confidence: 99%

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Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Couto

Duarte

Fernandez

et al. 2007

J. Am. Soc. Mass Spectrom.

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Most complexes of azides and transition metals involve the N 3Ϫ azide anion as a ligand other than an organic azide. Complexes of organic azides with metals are involved in biological applications and in the deposition of nitrenes on metal surfaces, producing nitride layers for semi-conductors preparation; this makes the study of these interactions an important issue. This work describes a study of the complexation of nickel and cobalt by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl 2 and CoCl 2 in methanol/water. In the case of nickel, other NiX 2 salts were investigated (where X ϭ Br or NO 3 ) and other solvents were also studied (notably ethanol/water). All complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N 2 , and HCN being quite common. The most abundant cations observed were [Ni(II)AzAzX] ϩ , where X ϭ Cl, Br, NO 3 . Some of the complexes showed solvation with methanol/ethanol/water. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metalOnitrogen bond. Collision induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions observed from the fragmentation routes were explained by a proposed gas-phase mechanism. Density functional theory calculations were carried out and provided structures for some complexes, pointing to the possibility of 3-azidopropionitrile acting as a mono-or a bidentate ligand. (J Am Soc Mass Spectrom 2007, 18, 453-465)

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Section: Esi-msástudiesáofácu(ii)-ureaácomplexáformationáalso Reportementioning

confidence: 99%

Section: Theoretical Studymentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

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Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Couto

Duarte

Fernandez

et al. 2007

J. Am. Soc. Mass Spectrom.

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“…This therapeutic action of AZT was due to its ability to inhibit reverse transcriptase enzyme. On the other hand, organoazido‐metal complexes are intermediates in the generation of metal imido complexes (MNR) whose chemistry is relevant 16–19. In addition, organoazido‐metal complexes are also intermediates in the synthesis of azomethines, cross‐linking of polymeric systems transition‐metal‐mediated reactions of azides 20…”

Section: Introductionmentioning

confidence: 99%

Azidoacetone as a complexing agent of transition metals Ni²⁺/Co²⁺ promoted dissociation of the CC bond in azidoacetone

Assis¹,

Couto²,

Duarte³

et al. 2011

J. Mass Spectrom.

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The relevance of metal interactions with azides has led us to the study of the complexation of some transition metals, nickel and cobalt, by azidoacetone by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl(2) and CoCl(2) , in methanol/water. Nickel was electrosprayed with other counter ion, bromide (Br), as well as other solvent (ethanol/water). For nickel and cobalt, the complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N(2) being quite common. The most abundant species were [Ni(II)Az(2)X](+) where X = Cl, Br and Az = azidoacetone. Some of the complexes showed solvation with the solvent components. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metal coordination bond. Collision-induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions of the fragmentation routes were explained by a gas-phase mechanism proposed where a C-C bond was activated and the metal inserted subsequently. Density functional theory calculations provided structures for some complexes. In [Ni(II)Az(2)X](+) species, one azidoacetone ligand is monodentate and the dominant binding location is the alkylated nitrogen and not the carbonyl group. The other azidoacetone ligand is bidentate showing coordination through alkylated nitrogen and the carbonyl group. These are also the preferential binding sites for the most stable isomer of [Ni(II)AzX](+) species.

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Sterically Controlled Pathways in the Reaction of 2,4,6-Tris(isopropyl)benzenesulfonyl Azide and [Pd2Cl2(dppm)2]

Besenyei¹,

Pa̋rkányi²,

Foch³

et al. 2000

Angewandte Chemie

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Organic azides often react with metal complexes with extrusion of N 2 , affording imido (nitrene) derivatives. [1] The azide moiety is not necessarily cleaved, however, as illustrated by earlier studies on hydridoosmium and dimeric molybdenum complexes. [2] Several aryl and cyclohexyl azide complexes revealing various modes of coordination have recently been characterized structurally and chemically. [3] Our previous work on the phosgene-free synthesis of isocyanates has shown that arenesulfonyl azides react with [Pd 2 Cl 2 (dppm) 2 ] (1, dppm bis(diphenylphosphanyl)methane), resulting in the formation of arylsulfonylimido A-frame adducts. [4,5] These novel reactions show good selectivities with most sulfonyl azides, except for the 2-nitro derivative, which gave [Pd 2 Cl 2 (dppm) 2 (N 3 SO 2 C 6 H 4 -2-NO 2 )] as a by-product. [5a] To elucidate the steric effects of azide ligands, we conducted studies with 2,4,6-tris(isopropyl)benzenesulfonyl azide (TipSO 2 N 3 , 2). The results of these investigations, together with crystallographic data on the parent azide 2, are presented here.Reaction of [Pd 2 Cl 2 (dppm) 2 ] with 2 affords the azide complex 3 and the nitrene complex 4 in 75 and 25 % yield, respectively [Eq. (1); 1 H NMR, see the Experimental Section], involving a very bulky bridging imido ligand. The 2 [Pd 2 Cl 2 (dppm) 2 ] 2 TipSO 2 N 3 ÀN2 3 1 2 [Pd 2 Cl 2 (dppm) 2 (m,h 1 -N 3 SO 2 Tip)] [Pd 2 Cl 2 (dppm) 2 (m-NSO 2 Tip)](1)3 4 molecular structures of the complexes formed are shown in Figures 1 and 2. The products are typical A-frame adducts with an extended boat conformation of the Pd 2 P 4 C 2 ring. The PdÀPd distances are about 0.6 longer than in [Pd 2 Br 2 (dppm) 2 ], ruling out metal ± metal bonding. [6] The redistribution of valence electrons induced by coordination can be best visualized by comparing bond lengths in free and coordinated sulfonyl azide. Although N3 is disordered in 2 (structure not shown, the numbering corresponds to that of 3), the short N1ÀN2 and N2ÀN3 bonds (1.213(3) and 1.14 ) indicate multiple bonding, in line with structural data for other sulfonyl azides. [7] Decreased bond orders as a result of complexation are clear from the N2ÀN3 and N1ÀN2 distances of 1.248(5) and 1.340(5) in 3. The structural features of 3 are consistent with 2 reacting as a 1,3-dipole (ArÀSO 2 ÀN À ÀNN ), producing a zwitterionic structure with the negative charge delocalized on the N1ÀN2 and N1ÀS1 bonds. The azide-to-sulfonyl electron transfer shortens the Figure 1. Molecular structure of 3 without hydrogen atoms. Selected interatomic distances [] and angles [8]:

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Transition Metal Complexes with Organoazide Ligands: Synthesis, Structural Chemistry, and Reactivity

Cited by 79 publications

References 4 publications

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Azidoacetone as a complexing agent of transition metals Ni²⁺/Co²⁺ promoted dissociation of the CC bond in azidoacetone

Sterically Controlled Pathways in the Reaction of 2,4,6-Tris(isopropyl)benzenesulfonyl Azide and [Pd2Cl2(dppm)2]

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Transition Metal Complexes with Organoazide Ligands: Synthesis, Structural Chemistry, and Reactivity

Cited by 79 publications

References 4 publications

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study

Azidoacetone as a complexing agent of transition metals Ni2+/Co2+ promoted dissociation of the CC bond in azidoacetone

Sterically Controlled Pathways in the Reaction of 2,4,6-Tris(isopropyl)benzenesulfonyl Azide and [Pd2Cl2(dppm)2]

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Azidoacetone as a complexing agent of transition metals Ni²⁺/Co²⁺ promoted dissociation of the CC bond in azidoacetone