Syntheses and structures of an unsolvated tetrakisimidophosphate {Li3[P(NBut)3(NSiMe3)]}2 and the face-sharing double-cubane {Li2(THF)[P(O)(NBut)2(NHBut)]}2

Armstrong, Andrea; Chivers, Tristram; Krahn, Mark; Parvez, Masood; Schatte, Gabriele

doi:10.1039/b207197e

Cited by 34 publications

(34 citation statements)

References 20 publications

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“…31 Rather This disparity is attributed to the different electronic environment at the phosphorus center due to the linear PNSi unit of 2b, 13 as discussed earlier for 1b and 1c. The 7 Li NMR spectrum of 2a consists of a broad resonance spanning approximately 4 ppm, suggesting that the lithium cations are dynamic in THF solutions.…”

Section: Detailsmentioning

confidence: 85%

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Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)₃(NR‘)]^•^2-

et al. 2005

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The reaction of Cl 3 PNSiMe 3 with 3 equiv of LiHNR (R ) i Pr, Cy, t Bu, Ad) in diethyl ether produces the corresponding tris(amino)(imino)phosphoranes (RNH) 3 PNSiMe 3 (1a, R ) i Pr; 1b, R ) Cy; 1c, R ) t Bu; 1d, R ) Ad); subsequent reactions of 1b−d with n BuLi yield the trilithiated tetraimidophosphates {Li 3 [P(NR) 3 (NSiMe 3 )]} (2a, R ) Cy; 2b, R ) t Bu; 2c, R ) Ad). The reaction of [( t BuNH) 4 P]Cl with 1 equiv of n BuLi results in the isolation of ( t BuNH) 3 PN t Bu (1e); treatment of 1e with additional n BuLi generates the symmetrical tetraimidophosphate {Li 3 [P(N t Bu) 4 ]} (2d). Compounds 1 and 2 have been characterized by multinuclear ( 1 H, 13 C, and 31 P) 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 {Li 2 [P(NR) 3 (NSiMe 3 )]LiX•3THF} • (X ) Cl, Br, I; R ) t Bu, Ad). The stable radicals exhibit C 3 symmetry and are thought to exist in a cubic arrangement, with the monomeric LiX unit bonded to the neutral radical {Li 2 [P(NR) 3 (NSiMe 3 )]} • to complete the Li 3 N 3 PX cube. Reactions of solventseparated ion pair {[Li(THF) 4 ]{Li(THF) 2 [(µ-N t Bu) 2 P(µ-N t Bu) 2 ]Li(THF) 2 } (6) with I 2 or SO 2 Cl 2 produce the persistent spirocyclic radical {(THF) 2 Li(µ-N t Bu) 2 P(µ-N t Bu)Li(THF) 2 } • (10a); all radicals have been characterized by a combination of variable concentration EPR experiments and DFT calculations.

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Section: Detailsmentioning

confidence: 85%

“…13 The one-electron oxidation of 2b with bromine or iodine has resulted in the isolation of the stable neutral radicals {Li2[P(N t Bu)3(NSiMe3)]•LiX•3THF} • (3b, X = Br; 3c, X = I);…”

Section: Introductionmentioning

confidence: 99%

Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)₃(NR‘)]^•^2-

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“…[17] However, no reactions of this important member of the family of p-block polyimido anions have been reported. Our recent discovery of a simple and versatile route to tetrakisimidophosphates, for example, [{Li 3 [P(NtBu) 3 -(NSiMe 3 )]} 2 ] (1), [18] has facilitated investigations of the chemistry of these isoelectronic analogues of the orthophosphate PO 4 3À ion. We describe here the synthesis of the stable, neutral radicals [Me 3 SiNP(m 3 -NtBu) 3 {m 3 -Li(thf)} 3 X]C (2 a, X = Br; 2 b, X = I) obtained by the oxidation of 1 with halogens.…”

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Stable Cubic Phosphorus‐Containing Radicals

et al. 2004

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“…The chemical and physical properties of these polyimido anions are dependent in large part upon the ratio of imido:oxo units and the size of the imido substituent. 1 Numerous analogues of phosphorus oxo-anions have been prepared, 3 including the trisimido(meta)phosphate 4 Previously we have thoroughly investigated the reactivities of a series of trisaminophosphates OP(NH t Bu)3 (1), 6,8 SP(NHR)3 (2a, R = t Bu; 2b, R = i Pr; 2c, R = ptol) 8,10 and (RNH)3PNSiMe3 (3a, R = t Bu; 3b, R = Cy) 6, 11 toward alkyllithium reagents.…”

Section: Introductionmentioning

confidence: 99%

“…Iodine was sublimed prior to use. (RNH)3PNSiMe3 (R = t Bu, Cy), 6 SP(NH t Bu)3 8 and OP(NH t Bu)3 8 were prepared as described previously.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates: EPR and DFT Investigations of the Persistent Neutral Radicals {Me₂Al[(μ-NR)(μ-N^tBu)P(μ-N^tBu)₂]Li(THF)₂}^• (R = SiMe₃, ^tBu)

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Reactions of (RNH)3PNSiMe3 (3a, R = t Bu; 3b, R = Cy) with trimethylaluminum result in the formation of {Me2Al(μ-N t Bu)(μ-NSiMe3)P(NH t Bu)2]} (4) and the dimeric trisimidometaphosphate {Me2Al[(μ-NCy)(μ-NSiMe3)P(μ-NCy)2P(μ-NCy)(μ-NSiMe3)]AlMe2} (5a), respectively. The reaction of SP(NH t Bu)3 (2a) with 1 or 2 equiv of AlMe3 yields {Me2Al[(μ-S)(μ-N t Bu)P(NH t Bu)2]} (7) and {Me2Al[(μ-S)(μ-N t Bu)P(μ-NH t Bu)(μ-N t Bu)]AlMe2} (8), respectively. Metalation of 4 with n BuLi produces the heterobimetallic species {Me2Al[(μ-N t Bu)(μ-NSiMe3)P(μ-NH t Bu)(μ-N t Bu)]Li(THF)2} (9a) and {[Me2Al][Li]2[P(N t Bu)3(NSiMe3)]} (10) sequentially; in THF solutions, solvation of 10 yields an ion pair containing a spirocyclic tetraimidophosphate monoanion. Similarly, the reaction of ( t BuNH)3PN t Bu with AlMe3 followed by 2 equiv of n BuLi generates {Me2Al[(μ-N t Bu)2P(μ2-N t Bu)2(μ2-THF)[Li(THF)]2} (11a). Stoichiometric oxidations of 10 and 11a with iodine yield the neutral spirocyclic radicals {Me2Al[(μ-NR)(μ-N t Bu)P(μ-N t Bu)2]Li(THF)2}• (13a, R = SiMe3; 14a, R = t Bu), which have been characterized by electron paramagnetic resonance spectroscopy. Density functional theory calculations confirm the retention of the spirocyclic structure and indicate that the spin density in these radicals is concentrated on the nitrogen atoms of the PN2Li ring. When 3a or 3b is treated with 0.5 equiv of dibutylmagnesium, the complexes {Mg[(μ-N t Bu)(μ-NH t Bu)P(NH t Bu)(NSiMe3)]2} (15) and {Mg[(μ-NCy)(μ-NSiMe3)P(NHCy)2]2} (16) are obtained, respectively. The addition of 0.5 equiv of MgBu2 to 2a results in the formation of {Mg[(μ-S)(μ-N t Bu)P(NH t Bu)2]2} (17), which produces the hexameric species {[MgOH][(μ-S)(μ-N t Bu)P(NH t Bu)2]}6 (18) upon hydrolysis. Compounds 4, 5a, 7−11a, and 15−17 have been characterized by multinuclear (1H, 13C, and 31P) NMR spectroscopy and, in the case of 5a, 9a·2THF, 11a, and 18, by X-ray crystallography.

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Syntheses and structures of an unsolvated tetrakisimidophosphate {Li3[P(NBut)3(NSiMe3)]}2 and the face-sharing double-cubane {Li2(THF)[P(O)(NBut)2(NHBut)]}2

Cited by 34 publications

References 20 publications

Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)₃(NR‘)]^•^2-

Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)₃(NR‘)]^•^2-

Stable Cubic Phosphorus‐Containing Radicals

Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates: EPR and DFT Investigations of the Persistent Neutral Radicals {Me₂Al[(μ-NR)(μ-N^tBu)P(μ-N^tBu)₂]Li(THF)₂}^• (R = SiMe₃, ^tBu)

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Syntheses and structures of an unsolvated tetrakisimidophosphate {Li3[P(NBut)3(NSiMe3)]}2 and the face-sharing double-cubane {Li2(THF)[P(O)(NBut)2(NHBut)]}2

Cited by 34 publications

References 20 publications

Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)3(NR‘)]•2-

Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)3(NR‘)]•2-

Stable Cubic Phosphorus‐Containing Radicals

Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates: EPR and DFT Investigations of the Persistent Neutral Radicals {Me2Al[(μ-NR)(μ-NtBu)P(μ-NtBu)2]Li(THF)2}• (R = SiMe3, tBu)

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Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)₃(NR‘)]^•^2-

Cubic and Spirocyclic Radicals Containing a Tetraimidophosphate Dianion [P(NR)₃(NR‘)]^•^2-

Synthesis and Structures of Aluminum and Magnesium Complexes of Tetraimidophosphates and Trisamidothiophosphates: EPR and DFT Investigations of the Persistent Neutral Radicals {Me₂Al[(μ-NR)(μ-N^tBu)P(μ-N^tBu)₂]Li(THF)₂}^• (R = SiMe₃, ^tBu)