Preparation and Structure of a Diphosphorus Compound with Positive Charges on the Two Directly Bonded Phosphorus Atoms

Schomburg, Dietmar; Bettermann, Gerhard; Ernst, Ludger; Schmutzler, Reinhard

doi:10.1002/anie.198509751

Cited by 43 publications

(17 citation statements)

References 5 publications

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“…The structural features of the cation are also consistent with the diphosphonium model 4 ( Me)b , with P−P bond lengths (2.138(7) and 2.156(10) Å) comparable to that of the novel diphosphonium cation 9 (2.189 Å) and to other P V −P V bonds (e.g. Me 2 P(S)−P(S)Me 2 , 2.245(6) Å; Me 2 P(BH 3 )−P(BH 3 )Me 2 , 2.189(5) Å 41 ).…”

Section: Resultssupporting

confidence: 67%

Structural Alternatives in R₂(Cl)P:GaCl₃ Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

et al. 1997

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Systematic NMR studies of (dialkyl/diaryl)chlorophosphine−gallium chloride reaction mixtures reveal three structural alternatives, which are related by equilibria in solution, and their relative stability is dependent on the nature of the substituent (R = Me, Et, iPr, tBu, Ph) and the reaction stoichiometry. The coordination complex R2(Cl)P→GaCl3 is observed in all cases, and a derivative (R = iPr) has been crystallographically characterized. Tetrachlorogallate salts of the diphosphorus cations [R2(Cl)P−PR2]+ are observed for smaller R substituents (R = Me, Et, iPr, Ph), consistent with a previous report. Solid-state 31P CP-MAS NMR spectra distinguish the methyl derivative from the novel salt [Me2(Cl)P−P(Me2)−GaCl3][GaCl4], containing a phosphine−phosphenium−gallium chloride cation, which has been crystallographically characterized. Factors governing the relative stabilities of the structural alternatives are discussed, and comparisons are made between the isomeric forms for R2(Cl)P:GaCl3.

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Section: Resultssupporting

confidence: 67%

Structural Alternatives in R₂(Cl)P:GaCl₃ Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

et al. 1997

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“…The transannular P3–P6 distance exhibits the most significant change relative to 1 , decreasing by 0.65 Å. Upon removal of a second electron 1 2+ , this distance is further shortened to 2.25 Å, a value in good agreement with those found in the diphosphonium salts 4–6 .…”

Section: Resultssupporting

confidence: 82%

“…In addition, there are several examples of structurally characterized dications in which two phosphonium centers are directly linked. In some cases, the positive charge on the P atoms is stabilized by delocalization over amino substituents resulting in short P–N bonds . However, a number of diphosphonium salts with only P–C bonds have also been described, e.g., 4 , 5 and 6 .…”

Section: Introductionmentioning

confidence: 99%

“…Compound 5 is shown as the hexamethyl derivative, but several other examples of diphosphonium salts with various combinations of alkyl groups on the P atoms have been structurally characterized. With one exception, the P–P bond length in these diphosphonium systems falls within the range 2.16–2.25 Å typical of single‐bond values in catenated phosphorus compounds; the exception is [(Et 2 N) 3 P–P(NEt 2 ) 3 ] 2+ for which the P–P distance is 2.364(3) Å . In the light of these precedents, we were stimulated to consider whether the cation radical 1 +• or the dication 1 2+ might be stabilized by a transannular P–P interaction.…”

Section: Introductionmentioning

confidence: 99%

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Structural Changes Upon Oxidation of (P^tBu₂)₂ and 1,4‐(CH₂)₂(P^tBu)₄: Transannular P–P Interactions in Cations of the 1,4‐C₂P₄ Ring

Elder

Roemmele

Taghavikish

et al. 2014

Heteroatom Chemistry

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“…13 A seminal paper from Schmutzler reported a 1,2-diphosphonium with a remarkably high magnitude of 1 J PP coupling of 219 Hz; however, this example is electronically and structurally very dissimilar to our species 10 and 11. 15 Hence, 11 has a magnitude of 1 J PP coupling constant at the low end of the reported range, while 10 exhibits the lowest magnitude of 1 J PP coupling reported among 1,2-diphosphoniums so far. Heteroleptic Bis(phosphines) 12 and 13 and Their Molybdenum(0) Complexes 14 and 15.…”

Section: ■ Results and Discussionmentioning

confidence: 81%

peri-Substituted Phosphino-Phosphonium Salts: Synthesis and Reactivity

et al. 2013

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The clean reaction of 5-lithio-6-(diisopropylphosphino)acenaphthene with dichlorophosphines RPCl2 gives the peri-substituted phosphino-phosphonium salts [Acenap(PiPr2)(PR)]+Cl– (2, R = Ph; 3, R = Fc; 4, R = NMe2; 5, R = iPr; Acenap = acenaphthene-5,6-diyl). Their ionic structure is maintained in solution and in the solid state. The reduction of 2 and 3 with LiAlH4 led to the formation of mixed tertiary/secondary chelating bis(phosphines) Acenap(PiPr2)(PRH) (6 and 7), which were subsequently reacted with PtCl2(cod) to give the complexes [(6)/(7)PtCl2] (8 and 9). Reaction of 2 and 3 with a large excess of MeOTf at elevated temperature gave the chiral 1,2-diphosphoniums [Acenap(PiPr2)(PRMe)]2+([TfO]−)2 (10 and 11), which were reduced with LiAlH4 to the heteroleptic bis(phosphines) Acenap(PiPr2)(PRMe) (12 and 13); these were then reacted with [(nor)Mo(CO)4] to give the complexes [(12)/(13)Mo(CO)4] (14 and 15). The heteroleptic bis(phosphines) 6, 7, 12, and 13 display large through-space couplings (formally 4 J PP = 163–199 Hz), comparable in magnitude to 1 J PP couplings observed in phosphino-phosphonium salts 2–5 (303–412 Hz). Single-crystal X-ray structures of 2, 3, 7–9, 14, and 15 are reported.

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Preparation and Structure of a Diphosphorus Compound with Positive Charges on the Two Directly Bonded Phosphorus Atoms

Cited by 43 publications

References 5 publications

Structural Alternatives in R₂(Cl)P:GaCl₃ Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Structural Alternatives in R₂(Cl)P:GaCl₃ Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Structural Changes Upon Oxidation of (P^tBu₂)₂ and 1,4‐(CH₂)₂(P^tBu)₄: Transannular P–P Interactions in Cations of the 1,4‐C₂P₄ Ring

peri-Substituted Phosphino-Phosphonium Salts: Synthesis and Reactivity

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Preparation and Structure of a Diphosphorus Compound with Positive Charges on the Two Directly Bonded Phosphorus Atoms

Cited by 43 publications

References 5 publications

Structural Alternatives in R2(Cl)P:GaCl3 Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Structural Alternatives in R2(Cl)P:GaCl3 Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Structural Changes Upon Oxidation of (PtBu2)2 and 1,4‐(CH2)2(PtBu)4: Transannular P–P Interactions in Cations of the 1,4‐C2P4 Ring

peri-Substituted Phosphino-Phosphonium Salts: Synthesis and Reactivity

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Structural Alternatives in R₂(Cl)P:GaCl₃ Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Structural Alternatives in R₂(Cl)P:GaCl₃ Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Structural Changes Upon Oxidation of (P^tBu₂)₂ and 1,4‐(CH₂)₂(P^tBu)₄: Transannular P–P Interactions in Cations of the 1,4‐C₂P₄ Ring