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Chivers, Ian

doi:10.1007/978-1-4471-0075-1_9

Cited by 2 publications

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“…X-ray Structure of Li[P(N t Bu)(NH t Bu) 2 (NSiMe 3 )] (2). While imido analogues of numerous phosphorus oxoanions have been reported previously, complex 2 is the first imido derivative of dihydrogen phosphate [H 2 PO 4 ] - to be characterized in full. In contrast to the extended structures typically found in metal complexes of the [H 2 PO 4 ] - anion, an X-ray structural analysis revealed that 2 exists as a dimer in the solid state (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…The imido group is isoelectronic with the oxo [O] 2- substituent; replacement of one or more oxo ligands by an imido group generates a new class of p-block polyanions with significantly different chemical and physical properties than those of their parent oxo-anions. Numerous analogues of phosphorus oxo-anions have been prepared, including both homoleptic systems, in which all the oxo substituents have been replaced by imido groups, and heteroleptic compounds, which contain both oxo and imido moieties. Examples of polyimido-anions include trisimidometaphosphate ions [P(NR) 3 ] - , bisimidophosphinate ions [R 2 P(NR) 2 ] 2- , and the tetrakisimidophosphate trianion [P(NNaph) 4 ] 3- (Naph = naphthyl) .…”

Section: Introductionmentioning

confidence: 99%

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Lithiation of (^tBuNH)₃PNSiMe₃ and Formation of Tetraimidophosphate Complexes Containing M₃O₃ Rings (M = Li, K): X-ray Structure of the Stable Radical {(Me₃SiN)P(μ₃-N^tBu)₃[μ₃-Li(THF)]₃(O^tBu)}

et al. 2004

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The reaction of ((t)BuNH)(3)PNSiMe(3) (1) with 1 equiv of (n)BuLi results in the formation of Li[P(NH(t)Bu)(2)(N(t)Bu)(NSiMe(3))] (2); treatment of 2 with a second equivalent of (n)BuLi produces the dilithium salt Li(2)[P(NH(t)Bu)(N(t)Bu)(2)(NSiMe(3))] (3). Similarly, the reaction of 1 and (n)BuLi in a 1:3 stoichiometry produces the trilithiated species Li(3)[P(N(t)Bu)(3)(NSiMe(3))] (4). These three complexes represent imido analogues of dihydrogen phosphate [H(2)PO(4)](-), hydrogen phosphate [HPO(4)](2)(-), and orthophosphate [PO(4)](3)(-), respectively. Reaction of 4 with alkali metal alkoxides MOR (M = Li, R = SiMe(3); M = K, R = (t)Bu) generates the imido-alkoxy complexes [Li(3)[P(N(t)Bu)(3)(NSiMe(3))](MOR)(3)] (8, M = Li; 9, M = K). These compounds were characterized by multinuclear ((1)H, (7)Li, (13)C, and (31)P) NMR spectroscopy and, in the cases of 2, 8, and 9.3THF, by X-ray crystallography. In the solid state, 2 exists as a dimer with Li-N contacts serving to link the two Li[P(NH(t)Bu)(2)(N(t)Bu)(NSiMe(3))] units. The monomeric compounds 8 and 9.3THF consist of a rare M(3)O(3) ring coordinated to the (LiN)(3) unit of 4. The unexpected formation of the stable radical [(Me(3)SiN)P(mu(3)-N(t)Bu)(3)[mu(3)-Li(THF)](3)(O(t)Bu)] (10) is also reported. X-ray crystallography indicated that 10 has a distorted cubic structure consisting of the radical dianion [P(N(t)Bu)(3)(NSiMe(3))](.2)(-), two lithium cations, and a molecule of LiO(t)Bu in the solid state. In dilute THF solution, the cube is disrupted to give the radical monoanion [(Me(3)SiN)((t)BuN)P(mu-N(t)Bu)(2)Li(THF)(2)](.-), which was identified by EPR spectroscopy.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Lithiation of (^tBuNH)₃PNSiMe₃ and Formation of Tetraimidophosphate Complexes Containing M₃O₃ Rings (M = Li, K): X-ray Structure of the Stable Radical {(Me₃SiN)P(μ₃-N^tBu)₃[μ₃-Li(THF)]₃(O^tBu)}

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%

“…Numerous analogues of phosphorus oxoanions have been prepared, including the trisimido(meta)phosphate [P(NR) 3 ] - and tetraimido(ortho)phosphate [P(NR) 3 (NR‘)] 3- (R = R‘ = naphthyl; R = t Bu, R‘ = SiMe 3 ) trianions. Heteroleptic systems, such as the trisimidophosphate and -thiophosphate trianions [EP(NR) 3 ] 3- (E = O, S), have also been reported recently, and the first transition-metal derivatives of the sulfur-containing ligand have been characterized …”

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)

et al. 2005

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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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Lithiation of (^tBuNH)₃PNSiMe₃ and Formation of Tetraimidophosphate Complexes Containing M₃O₃ Rings (M = Li, K): X-ray Structure of the Stable Radical {(Me₃SiN)P(μ₃-N^tBu)₃[μ₃-Li(THF)]₃(O^tBu)}

Lithiation of (^tBuNH)₃PNSiMe₃ and Formation of Tetraimidophosphate Complexes Containing M₃O₃ Rings (M = Li, K): X-ray Structure of the Stable Radical {(Me₃SiN)P(μ₃-N^tBu)₃[μ₃-Li(THF)]₃(O^tBu)}

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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Lithiation of (tBuNH)3PNSiMe3 and Formation of Tetraimidophosphate Complexes Containing M3O3 Rings (M = Li, K): X-ray Structure of the Stable Radical {(Me3SiN)P(μ3-NtBu)3[μ3-Li(THF)]3(OtBu)}

Lithiation of (tBuNH)3PNSiMe3 and Formation of Tetraimidophosphate Complexes Containing M3O3 Rings (M = Li, K): X-ray Structure of the Stable Radical {(Me3SiN)P(μ3-NtBu)3[μ3-Li(THF)]3(OtBu)}

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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Lithiation of (^tBuNH)₃PNSiMe₃ and Formation of Tetraimidophosphate Complexes Containing M₃O₃ Rings (M = Li, K): X-ray Structure of the Stable Radical {(Me₃SiN)P(μ₃-N^tBu)₃[μ₃-Li(THF)]₃(O^tBu)}

Lithiation of (^tBuNH)₃PNSiMe₃ and Formation of Tetraimidophosphate Complexes Containing M₃O₃ Rings (M = Li, K): X-ray Structure of the Stable Radical {(Me₃SiN)P(μ₃-N^tBu)₃[μ₃-Li(THF)]₃(O^tBu)}

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)