Lithium Oligophosphanediides in the Li/PhPCl<sub>2</sub> System

Stein, Daniel; Dransfeld, Alk; Flock, Michaela; Rüegger, Heinz

doi:10.1002/ejic.200600571

Cited by 30 publications

(23 citation statements)

References 31 publications

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“…3) are ion triples, while an ion pair was observed in [Li(tmeda) 2 ][Li(tmeda)(P 3 Ph 3 )] (43). 31 P NMR studies supported the assumption that these structures are retained in solution [39].…”

Section: Dianionic Phosphorus-rich Chainsmentioning

confidence: 78%

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

Gómez‐Ruiz

Hey‐Hawkins

2011

Coordination Chemistry Reviews

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Section: Dianionic Phosphorus-rich Chainsmentioning

confidence: 78%

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

Gómez‐Ruiz

Hey‐Hawkins

2011

Coordination Chemistry Reviews

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“…More recent studies by HeyHawkins and Grützmacher have explored the structural properties and coordination chemistry of these compounds. [5,6] However, aside from transmetallations of the alkali metal salts of [PR] n 2-with a range of transition and main group metal precursors, yielding metallocyclic and heterocyclic products in which the [RP] n backbone is maintained, little investigation into the reactivity of the oligophosphanediides in their own right has been conducted. 1 multistep syntheses.…”

Section: Introductionmentioning

confidence: 99%

One‐Pot Synthesis of a 1,2‐Diphospholide by Double C–H Deprotonation

et al. 2015

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Rapid testing of hydrophilic and hydrophobic basic immobilized amine sorbents (BIAS) for CO2 capture stability under practical conditions was achieved by direct contact of the sorbents with flowing liquid water. Losses in both CO2 capture capacity and amine content of sorbents after exposure to 0.5 mL min−1 of H2O at 25 °C for 40 min followed similar trends as losses observed after exposure to N2/steam (105 °C, 7 % H2O) for 10 h. We also found that hydrophobic TMPED helped stabilize sorbents to H2O, which was confirmed by DRIFTS and combined TGA‐DSC.

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“…The solution was then filtered into a crystallization ampoule, layered with toluene, and left to crystallize. After several days, 26 Single-crystal X-ray diffraction data were collected using an Enraf-Nonius Kappa-CCD diffractometer and a 95 mm CCD area detector with a graphite-monochromated molybdenum K a source (l = 0.71073 ). Crystals were selected under Paratone-N oil, mounted on MiTeGen loops, and quench-cooled using an open flow N 2 cooling device.…”

Section: Methodsmentioning

confidence: 99%

“…[25] Thus it can be rationalized as a singly bonded diphosphandiide dianion that is contracted somewhat owing to the reduction of electrostatic repulsion between phosphorus atoms (for comparison, the P À P distance in the lithium salt of diphenylphosphandiide is 2.244(3) ). [26] Alternatively, it can be interpreted in terms of extensive pbackbonding from a very electron-rich Co ÀI center into the p*-antibonding LUMO of a diphosphene. The DFT-optimized geometries for 1 with both cis-and trans-P 2 H(mes) moieties show bond metrics that are closely related to the crystallographically determined structure (see the Supporting Information for further details).…”

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confidence: 99%

[Co(η⁵‐P₅){η²‐P₂H(mes)}]²⁻: A Phospha‐Organometallic Complex Obtained by the Transition‐Metal‐Mediated Activation of the Heptaphosphide Trianion

et al. 2012

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The chemical activation of white phosphorus by transitionmetal complexes is a versatile albeit often unpredictable route to compounds containing homoatomic phosphorus ligands with nuclearities ranging between 1 and 29. [1] In principle, many of the same transformations available for P 4 should also be possible employing other closely related cage compounds, such as the bare Group 15 Zintl anion [P 7 ] 3À , although the products resulting from the activation of these anionic cages have little in common with those typically observed for white phosphorus. In most instances, heptapnictide [E 7 ] 3À anions (E = P, As, Sb) react with metal reagents by maintaining their structure and nuclearity or undergoing the activation of a single EÀE bond, resulting in a geometric change of the starting nortricyclane-like cage (C 3v ) to a geometry reminiscent of norbornadiene (C 2v ). [2,3] More extensive [E 7 ] 3À activation reactions have been reported on a handful of occasions for the heavier Group 15 elements (E = As, Sb), yielding species with increased cluster nuclearities and often unprecedented geometries. [3][4][5][6][7][8][9][10] Such transformations are entirely without precedent for the [P 7 ] 3À cage, however, which is presumably due to the greater bond dissociation energy of the P À P single bond. [11] Herein we report the chemical activation of the heptaphosphide trianion, [P 7 ] 3À , by the transition-metal complex [Co(mes) 2 (PEt 2 Ph) 2 ] (mes = 2,4,6-trimethylphenyl) to yield the novel anionic species [Co(h 5 -P 5 ){h 2 -P 2 H(mes)}] 2À (1; Figure 1). To our knowledge, this reaction is the first example of a transformation involving the chemical activation of an [E 7 ] 3À cage where the nuclearity of the heptaphosphide starting material remains the same but where a significant alteration of the nortricyclane-like cage geometry has resulted. The chemical activation of neutral systems with related topologies has been reported previously. [12] Coordination to the cobalt metal center has allowed us to "trap" the known cyclopentaphosphide ligand [P 5 ] À alongside the diphosphene-like moiety P 2 H(mes). The isolobal relationship between phosphorus atoms and CÀH fragments has led to phosphorus being referred to as the carbon copy. [13] This relationship makes [Co(h 5 -P 5 ){h 2 -P 2 H(mes)}] 2À a model system for the unknown family of anionic 18-electron organometallic complexes [Co(h 5 -C 5 H 5 )(h 2 -H 2 C = CHR)] 2À , which are in turn closely related to cobalt(I) bis(alkene) complexes, such as [CpCo(cod)] (cod = 1,5-cyclooctadiene) and Jonass reagent. [14, 15] Reaction of an ethylenediamine (en) solution of K 3 P 7 with one molar equivalent of [Co(mes) 2 (PEt 2 Ph) 2 ] yielded the heteroatomic ion [Co(h 5 -P 5 ){h 2 -P 2 H(mes)}] 2À . Monitoring of the crude reaction mixture by 31 P NMR spectroscopy reveals the presence of other minor unidentified phosphorus-containing side-products in addition to [Co(h 5 -P 5 ){h 2 -P 2 H-(mes)}] 2À . The [Co(h 5 -P 5 ){h 2 -P 2 H(mes)}] 2À cluster anion can be isolated as a pu...

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Lithium Oligophosphanediides in the Li/PhPCl₂ System

Cited by 30 publications

References 31 publications

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

One‐Pot Synthesis of a 1,2‐Diphospholide by Double C–H Deprotonation

[Co(η⁵‐P₅){η²‐P₂H(mes)}]²⁻: A Phospha‐Organometallic Complex Obtained by the Transition‐Metal‐Mediated Activation of the Heptaphosphide Trianion

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Lithium Oligophosphanediides in the Li/PhPCl2 System

Cited by 30 publications

References 31 publications

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

One‐Pot Synthesis of a 1,2‐Diphospholide by Double C–H Deprotonation

[Co(η5‐P5){η2‐P2H(mes)}]2−: A Phospha‐Organometallic Complex Obtained by the Transition‐Metal‐Mediated Activation of the Heptaphosphide Trianion

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Lithium Oligophosphanediides in the Li/PhPCl₂ System

[Co(η⁵‐P₅){η²‐P₂H(mes)}]²⁻: A Phospha‐Organometallic Complex Obtained by the Transition‐Metal‐Mediated Activation of the Heptaphosphide Trianion