Transition Metal Complexes of Diazenes, XVII [1]. Reactions of 1,2-Diazetines and 1,2-Diazetine-N-oxides with Iron Carbonyls

Albini, Angelo; Kisch, Horst; Chiang, An-Pei

doi:10.1515/znb-1982-0412

Cited by 9 publications

(2 citation statements)

References 11 publications

(16 reference statements)

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“…[27] Tetrazolidine 38a (methyl group in front) [the b-isomer (methyl group at the back) is clearly less stable] was approached following the protocol successfully applied to the azomethine/ene cycloaddition [1][28] -by methylation (35a,b) and deprotonation (36a,b) (Scheme 5). In the preparative protocol ultimately followed, bisdiazene 1a was treated with equimolar amounts of trimethyloxonium tetrafluoroborate (34). The crude, complex mixture of salts and 1a was fractionally crystallized, and the main fraction (50-60%, 37a) was exposed to the K 2 CO 3 /H 2 O/CH 2 Cl 2 two-phase system.…”

Section: Homoconjugate Reactivity -Cycloadditionsmetal Complexesmentioning

confidence: 99%

“…[4d] Searching for complexes of 1a which might be amenable to double bridging [5d] e.g. by internal substitution or thermal activation, [34] an initially promising complex was found when 1a was treated with norbornadienyl-rhodium(I) chloride dimer in boiling CH 3 CN. [5g] From the deeply red solution, black crystals of composition 1a*(NBD-Rh(I)-Cl) 2 , suitable for X-ray analysis (Figure 8), [25] deposited upon cooling to room temperature.…”

Section: Full Papermentioning

confidence: 99%

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Proximate,syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry

Exner¹,

Fischer

Bahr

et al. 2000

Eur. J. Org. Chem.

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Rigid NN/NN (diazene/diazene) systems (F) consisting of more or less alkylated DBH and DBO chromophoric units (1, 2, X‐ray structures), with very short π,π distances [d = 2.849 (1a, av.), 2.822 Å (2)] and almost perfect syn‐periplanar π,π alignments [ω = 168.6 (1a), 174.2° (2)] as well as the more flexible, less “proximate” metathesis isomers (3a,c, 27a,c, d >4.6 Å, ω = 90‐100°) have been synthesized. Homoconjugate π,π interaction (in 1, 2, not in 3, 27) is deduced from UV spectroscopic measurements [π → π* maxima at 239 (234) nm (sh, 260)], while PE analyses furnished only small interaction parameters (1a: <0.3 eV). The potential of the novel syn‐periplanar NN/NN motif in 1 and 2 for the synthesis of somewhat exotic polyheterocycles has been explored by calculation (B3LYP) as well as experimentally: i.a. kinetically stabilized, all‐cis‐peralkylated tetrazolidines (38, 44) and perhydro‐1,2,4,5‐tetrazines (41, 47) have become accessible (i.a. via novel azomethine/diazene and azomethine/azomethine cycloadditions). In 1a with its unreactive DBO chromophoric subunits, in the “buttressed” derivatives 1b‐d, as well as in the DBH/DBO combination 2, and likewise in more ‘distant’ 27 (differently from the analogous CC/CC and NN/CC systems), irrespective of the excitation conditions employed (light of λ ≥≥ 280, 254 nm, low temperature matrix irradiation, acetone sensitization) no [2+2]photocycloaddition was observed. Instead exclusively N2‐elimination took place. It is argued that unproductive NN/NN photocycloaddition would have become observable through metathesis isomerization of the respective tetrazetidines.

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Section: Homoconjugate Reactivity -Cycloadditionsmetal Complexesmentioning

confidence: 99%

Section: Full Papermentioning

confidence: 99%

Proximate,syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry

Exner¹,

Fischer

Bahr

et al. 2000

Eur. J. Org. Chem.

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syn1‐Periplanar Bisazo Skeletons — Syntheses and Reactions with Carbonylmetal Complexes

et al. 1993

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Preparatively useful synthesis for the novel, relatively mobile polycyclic syn1‐periplanar bisazo polycycles 4 and 5 are based on hydrazine condensation with readily available dienedione 6 and acid‐catalyzed rearrangement of bisurazole 12, respectively. In the preferred “closed” and “open” conformations of 4 and 5 the NN bonds are 314 and 496 pm, respectively, apart (MMX). From the reactions of 4 and 5 with carbonyliron and ‐ruthenium compounds, complexes are derived which are typical of monoazo ligands [4 · Fe(CO)4  20, 4 · Fe2(CO)721, 4 · Fe3(CO)922, 4[Fe2(CO)6]223, 4 · Ru3(CO)9 · 24, 5 · [Fe2(CO)6]2  25, 5 · Fe2(CO)6 · Fe3(CO)9  26]. For 21, 23 and 26 crystal structure analyses were performed, confirming i.a. in 26 the unique presence of a Fe2(CO)6 and a Fe3(CO)9 fragment attached to two azo units of the same molecule.

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Chromium, tungsten, iron, and ruthenium complexes of the 4-membered ring diazene 3,4-diazatricyclo[4.2.1.02,5]non-3-ene

Ackermann

Adams

Pranata

et al. 1989

Journal of Organometallic Chemistry

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Transition Metal Complexes of Diazenes, XVII [1]. Reactions of 1,2-Diazetines and 1,2-Diazetine-N-oxides with Iron Carbonyls

Cited by 9 publications

References 11 publications

Proximate,syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry

Proximate,syn-Periplanar Bisdiazene Skeletons: Syntheses, Structures, Homoconjugate Reactivity and Photochemistry

syn1‐Periplanar Bisazo Skeletons — Syntheses and Reactions with Carbonylmetal Complexes

Chromium, tungsten, iron, and ruthenium complexes of the 4-membered ring diazene 3,4-diazatricyclo[4.2.1.02,5]non-3-ene

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