Synthesis and x-ray structure of (2,2,6,6-tetramethyl-piperidinyl-1-oxo-O,N)tricarbonylmanganese(0); “side-on” coordination of the nitroxyl radical to manganese

Jaitner, Peter; Huber, Wolfgang; Hunter, G Douglas; Scheidsteger, Olaf

doi:10.1016/0022-328x(83)85163-8

Cited by 45 publications

(30 citation statements)

References 16 publications

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“…[152] Other transition-metal hydride complexes (rhodium and iridium hydrides) were also shown to react with TEMPO through H transfer to give TEMPOH and the corresponding metalloid radicals, which then undergo further reactions such as dimerization, addition to olefins, or homolytic substitution at the carbon atom. [153] Besides zinc-TEMPO complexes, other metal-TEMPO complexes of unsaturated transition metals (Mn, [154] Co, [155] Ni, [156] Cu, [157] Mo, [158] Ti, [159] and Pd [160] ) have been synthesized and fully characterized. Mg-TEMPO complexes were also prepared and studied by X-ray analysis.…”

Section: H Abstraction By Nitroxidesmentioning

confidence: 99%

Nitroxides: Applications in Synthesis and in Polymer Chemistry

2011

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This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.

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Section: H Abstraction By Nitroxidesmentioning

confidence: 99%

Nitroxides: Applications in Synthesis and in Polymer Chemistry

2011

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“…R = SiMe,. R ' = /Bu: W u t c \(>ii.MoIekiil h in Klammern 166.4( 14) 170.4 (13) 163.4 (13) 165.0 ( 13) …”

Section: 0(slc)mentioning

confidence: 99%

“…165.4 ( 13) 1 4 5 4 14) 165.0 (13) 177.5 (14) 187 ( 2) 119 ( 2) 157 ( 2 ) 166 ( 2) 159 ( 2) 256.8 (13) 211.3(14)…”

Section: 0(slc)unclassified

“…x l a 0.3651( 1) 0.2550 ( 3) 0.1848 ( 4) 0.0844 ( 4) 0.1433 ( 4) 0.3892 ( 5) 0.4799 ( 15) 0.4830 ( 9) 0.3486 ( 12) 0.4036 ( 1 2) 0.2556 ( 10) 0.2487 ( 9) 0.1770( 10) 0.21 36 ( 12) 0.3516( 10) 0 -4364 (22) 0.4354 ( 17) 0.3694 ( 2 1 ) 0.3846 ( 19) 0.2673 ( 12) 0.2226 ( 19) 0.2306 ( 1 7) 0.3539 ( 17) 0.2815 ( 14) 0.1163 ( 14) 0.1690 ( 15) 0.2506 ( 12) 0.2309 ( 14 ) 0.3353 ( 14) 0.2054 ( 15) 0.0238 (14) 0 -0424 ( 14) 0.0749 ( 15) 0.2608( 4) ( 9) 0.0491 ( 14) 0.0578 ( 12) -0.1120 ( 9 ) -0.2822( 10) -0.2264 ( 9) -0.0825 ( 15) -0.1137 ( 17) (20) 0.0176 ( 19) 0.0304 ( 13) -0.3295i t 3 j 'eq 4.2( 2) 7.1 ( 3) 13.3(11) 8.7 ( 7) 10.4 ( 9 ) 10.5( 9) 2.9( 5) 2.6( 4) 3.3( 5) 5.0( 6) 3.7( 5) 12.8 ( 13) 6.8( 9) ll.O(l3) 2.8( 6) 8.6( 10) 7.1( 9) 6.9 ( 9) 4.2( 7) 5.0( 7) 4.9( 7) 2.9( 6) 4.1( 7) 5.1( 7) 5.1( 7) 4.6( 7) 4.8( 7) 5.2( 7) 11.3( 13) 9.0(11) 11.6( 14)…”

Section: Rhenium(1)-komplexes [(Oc)reunclassified

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Elementorganische Amin/Imin‐Verbindungen, XXIX ¹⁾ [(OC) ₄ Re−NR− P(Cl)(NR ₂ )−NR], R = SiMe ₃ , ein vielseitiger Synthesebaustein

et al. 1987

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Die Cothermolyse von [(OC)dRk-NR-P(Cl)(NR2)-AR] (1) und RR'N-P=NR (2a: R = R = %Mes, 2b R = SiM+ R' = tBu) ergibt bei 2s neben dem Spirocyclus [RN-SiMe2-CH2 -(OC),Re -P-NR' -P(NR)(NHR) -kR'] (3a,b) den tricvclischen KomDIex 4. Die Substitution von 1 rnit LiCH2-SiMe3 (5) fiihrt zum fiinffach koordinierten d6-Rheniumkomplex [(OC)~R~-NR-P(CHIRXNR~)-~~R] (6), der mit (MeO),P Kohlenmonoxid-Substitution, mit f BuNC zusiitzlich Addition ergibt. 3b, 4 und 6 wurden durch Rontgenstrukturanalysen charak terisiert. Bei der Thermolyse von [(OC),Rk -NR -P(Cl)(NR,)-NR] (l), R = SiMe3, entstehen neben einer tricyclischen Phosphor-Dispiro-Rheniumverbindung der cubanartige Rheniumkomplex [Re2(CO)6(p3-NR)4(p3-PNR)z] sowie ein tetracyclischer Phosphor-Stickstoff-Rheniumkomplex'). P -Cl-Substitutionsreaktionen bei 1 a) Cothermolyse mit Amino(imino)phosphanen 1 und die Amino(imin0)phosphane 2 ergeben bei deren Cothermolyse die polycyclischen Phosphor-Stickstoff-Rheniumkomplexe 3 und 4.

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“…The sum of the three angles around P is 358.1°, indicating the contribution of π-bonding. Although 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its analogues are known to coordinate to the metal center in a κ 2 -(ON) coordination mode in the reaction with some transition metal complexes, 20 to the best of our knowledge, complex 4 is the first example of a structurally characterized nor-AZADO complex having a κ 2 -(ON) moiety. The overall reaction can be explained as follows: radical recombination between in situ -generated iron-centered radical 3 and the oxygen-centered radical takes place to create the Fe–O bond, followed by the liberation of one CO ligand from the iron center concomitant with the formation of the Fe–N bond.…”

Section: Introductionmentioning

confidence: 99%