Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)3(NR‘)]•2-
Armstrong, A., Chivers, T., Tuononen, H., Parvez, M., & Boeré, R. (2005). Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)3(NR‘)]•2-. Inorganic Chemistry, 44(22), 7981-7991. https://doi.org/10.1021/ic051128q
Julkaistu sarjassa
Inorganic ChemistryPäivämäärä
2005Tekijänoikeudet
© 2005 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
The reaction of Cl3PNSiMe3 with 3 equiv of LiHNR (R = iPr, Cy, tBu, Ad) in diethyl ether produces the corresponding tris(amino)(imino)phosphoranes (RNH)3PNSiMe3 (1a, R = iPr; 1b, R = Cy; 1c, R = tBu; 1d, R = Ad); subsequent reactions of 1b−d with nBuLi yield the trilithiated tetraimidophosphates {Li3[P(NR)3(NSiMe3)]} (2a, R = Cy; 2b, R = tBu; 2c, R = Ad). The reaction of [(tBuNH)4P]Cl with 1 equiv of nBuLi results in the isolation of (tBuNH)3PNtBu (1e); treatment of 1e with additional nBuLi generates the symmetrical tetraimidophosphate {Li3[P(NtBu)4]} (2d). Compounds 1 and 2 have been characterized by multinuclear (1H, 13C, and 31P) NMR spectroscopy; X-ray structures of 1b,c were also obtained. Oxidations of 2a−c with iodine, bromine, or sulfuryl chloride produces transient radicals in the case of 2a or stable radicals of the formula {Li2[P(NR)3(NSiMe3)]LiX·3THF}• (X = Cl, Br, I; R = tBu, Ad). The stable radicals exhibit C3 symmetry and are thought to exist in a cubic arrangement, with the monomeric LiX unit bonded to the neutral radical {Li2[P(NR)3(NSiMe3)]}• to complete the Li3N3PX cube. Reactions of solvent-separated ion pair {[Li(THF)4]{Li(THF)2[(μ-NtBu)2P(μ-NtBu)2]Li(THF)2} (6) with I2 or SO2Cl2 produce the persistent spirocyclic radical {(THF)2Li(μ-NtBu)2P(μ-NtBu)Li(THF)2}• (10a); all radicals have been characterized by a combination of variable concentration EPR experiments and DFT calculations.
...
Julkaisija
ACSISSN Hae Julkaisufoorumista
0020-1669Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/15539662
Metadata
Näytä kaikki kuvailutiedotKokoelmat
Samankaltainen aineisto
Näytetään aineistoja, joilla on samankaltainen nimeke tai asiasanat.
-
Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands
Brazeau, Allison; Hänninen, Mikko M.; Tuononen, Heikki; Jones, Nathan; Ragogna, Paul (ACS, 2012)The reported chemistry and reactivity of guanidinate supported group 15 elements in the +3 oxidation state, particularly phosphorus, is limited when compared to their ubiquity in supporting metallic elements across the ... -
Synthesis and Redox Behaviour of the Chalcogenocarbonyl Dianions, [(E)C(PPh2S)2]2−: Formation and Structures of Chalcogen−Chalcogen Bonded Dimers and a Novel Selone
Konu, Jari; Chivers, Tristram; Tuononen, Heikki (Wiley, 2010)The lithium salts of the chalcogenocarbonyl dianions [(E)C(PPh2S)2]2− (E=S (4 b), Se (4 c)) were produced through the reactions between Li2[C(PPh2S)2] and elemental chalcogens in the presence of tetramethylethylenediamine ... -
Bond Stretching and Redox Behavior in Coinage Metal Complexes of the Dichalcogenide Dianions [(SPh2P)2CEEC(PPh2S)2]2− (E=S, Se): Diradical Character of the Dinuclear Copper(I) Complex (E=S)
Konu, Jari; Chivers, Tristram; Tuononen, Heikki (Wiley, 2011)The metathetical reactions of a) [Li(tmeda)]2[(S)C(PPh2S)2] (Li2⋅3 c) with CuCl2 and b) [Li(tmeda)]2[(SPh2P)2CSSC(PPh2S)2] (Li2⋅4 c) with two equivalents of CuCl both afford the binuclear CuI complex {Cu2[(SPh2P)2CSSC(PPh2S)2]} ... -
Stable spirocyclic neutral radicals: aluminum and gallium boraamidinates
Chivers, Tristram; Eisler, Dana; Fedorchuk, Chantall; Schatte, Gabriele; Tuononen, Heikki; Boeré, René (RSC, 2005)Stable dark red (M = Al) or dark green (M = Ga) neutral radicals {[PhB(μ-NtBu)2]2M}˙ are obtained by the oxidation of their corresponding anions with iodine, and EPR spectra supported by DFT calculations show that the spin ... -
Experimental and Theoretical Investigations of Structural Isomers of Dichalcogenoimidodiphosphinate Dimers: Dichalcogenides or Spirocyclic Contact Ion Pairs?
Ritch, Jamie; Chivers, Tristram; Eisler, Dana; Tuononen, Heikki (Wiley, 2007)A synthetic protocol for the tert-butyl-substituted dichalcogenoimidodiphosphinates [Na(tmeda){(EPtBu2)2N}] (3 a, E=S; 3 b, E=Se; 3 c, E=Te) has been developed. The one-electron oxidation of the sodium complexes ...
Ellei toisin mainittu, julkisesti saatavilla olevia JYX-metatietoja (poislukien tiivistelmät) saa vapaasti uudelleenkäyttää CC0-lisenssillä.