Ein diphos‐Komplex von P⊕: das 1,1,3,3‐Tetraphenyl‐1λ5,2λ3,3λ5‐triphospholenyl‐Kation

Schmidpeter, Alfred; Lochschmidt, Siegfried; Sheldrick, William S.

doi:10.1002/ange.19820940120

Cited by 32 publications

(6 citation statements)

References 10 publications

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“…Compounds containing electron-rich (lone pair bearing) phosphorus(III) centers typically behave as ligands or Lewis bases in coordination chemistry. Nevertheless, a variety of complexes involving Lewis acceptor phosphorus(III) centers are known, and the formation of an E → P(III) coordinate bond (E = C, − N, − O, S, Se, P, − Ga 33 ) represents a new synthetic approach in phosphorus chemistry. The iminophosphine Mes*NPOTf (Mes* = 2,4,6-tri- tert -butylphenyl, OTf = trifluoromethanesulfonate, triflate) 34 is a particularly versatile reagent that engages ligands with consequential dissociation of the triflate anion.…”

Section: Introductionmentioning

confidence: 99%

Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands

et al. 2005

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Trifluoromethylsulfonyloxy-(2,4,6-tri-tert-butylphenylimino)phosphine, Mes*NPOTf (Mes = 2,4,6-tri-tert-butylphenyl, OTf = trifluoromethanesulfonate, triflate) reacts quantitatively with the multifunctional ligands 2,2'-bipyridine (2,2'-BIPY), N,N,N',N'-tetramethylethylenediamine (TMEDA), 1,2-bis(diethylphosphino)ethane (DEPE), 1,2-bis(diphenylphosphino)ethane (DIPHOS), and N,N,N',N' ',N' '-pentamethyldiethylenetriamine (PMDETA) to give the Lewis acid-base complexes [Mes*NP(2,2'-BIPY)][OTf], [Mes*NP(TMEDA)][OTf], [Mes*NP(DIPHOS)][OTf], [Mes*NP(DEPE)][OTf], and [Mes*NP(PMDETA)][OTf], respectively. Single-crystal X-ray diffraction studies indicate that the closest contact of the ligand donor atoms occurs at phosphorus in all cases, affecting significant displacement of the OTf anion. The resulting cations [Mes*NP(L)]+ are best described as complexes of a neutral chelating ligand on a phosphadiazonium Lewis acceptor, and highlight the potential for electron-rich centers to behave as Lewis acids despite the presence of a lone pair of electrons at the acceptor site. More importantly, the new complexes represent rare examples of systems containing hypervalent, low-coordinate phosphorus(III) centers.

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Section: Introductionmentioning

confidence: 99%

Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands

et al. 2005

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“…While the majority of the research into the chemistry of compounds containing group 15 elements in the +1 oxidation state has focused on P I , there has been limited development of As I chemistry. The first As I cation was reported by Gamper and Schmidbaur in 1993, which was prepared by the reduction of AsCl 3 with SnCl 2 in the presence of a chelating diphosphine; this approach is analogous to the method used by Schmidpeter et al to isolate their first P I cation . Similarly, Dillon and co-workers have recently used SnCl 2 to reduce AsCl 3 in solutions containing various chelating phosphines to produce salts that were identified by their 31 P NMR shifts and, for two compounds, by X-ray crystallography .…”

Section: Introductionmentioning

confidence: 99%

Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters

Ellis

Macdonald

2004

Inorg. Chem.

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The new stable low oxidation state arsenic(I) iodide reagent [(dppe)As][I] (dppe = 1,2-bis(diphenylphosphino)ethane) exhibits chemistry that is considerably different from its AsIII analogues. While [(dppe)As][I] is not crystalline, the crystal structure of the derivative salt [(dppe)As][(dppe)As2I7] is reported and is compared to that of [(dppe)As]2[SnCl6] x 2CH2Cl2. The air oxidation of [(dppe)As][I] produces crystals of the salt [Ph2P(O)CH2CH2P(OH)Ph2]2[As6I8] x 2CH2Cl2 and suggests that, in contrast to previous studies, the reaction of the univalent arsenic iodide salt with certain oxidants results in the oxidation of the dppe ligand and the release of "AsI-I" fragments that oligomerize to form AsI clusters. Such reactivity is confirmed by the reaction of 6[(dppe)As][I] with 12Me3NO and 2[PPh4][I] to produce [PPh4]2[As6I8] and 6dppeO2. The reactivity is rationalized using density functional theory calculations.

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“…The observed P−P bond lengths [for 1b + : P1−P2 2.1162(4) Å, 1c + : P1−P2 2.1195(4) Å, and 1d + : P1−P2 2.1446(4) Å] match values for related triphosphenium cations 19,23 and range between a typical P−P single 24 and P�P double bond. 25 This shortening has previously been attributed to result from ylidictype negative hyperconjugation between the lone pairs at the phosphanide moiety and the σ*(P−R) orbitals.…”

Section: ■ Introductionmentioning

confidence: 62%

“…Changing the ditopic phosphane to bis(diphenylphosphino)ethane (dppe) gives rise to a mixture of previously reported cyclic triphosphenium cation [(Ph 2 PC 2 H 4 PPh 2 )P] + and di(imidazoliumyl)phosphanide [(L C ) 2 P] + as evidenced by means of 31 P NMR spectroscopy (Scheme S3 and Figure S8). ,, …”

Section: Resultsmentioning

confidence: 99%

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Cationic Phosphinidene as a Versatile P₁ Building Block: [L_C–P]⁺ Transfer from Phosphonio–Phosphanides [L_C–P–PR₃]⁺ and Subsequent L_C Replacement Reactions (L_C = N-Heterocyclic Carbene)

et al. 2023

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Cationic imidazoliumyl(phosphonio)-phosphanides [L C −P−PR 3 ] + (1a−e + , L C = 4,5-dimethyl-1,3-diisopropylimidazolium-2-yl; R = alkyl, aryl) are obtained via the nucleophilic fragmentation of tetracationic tetraphosphetane [(L C −P) 4 ][OTf] 4 (2[OTf] 4 ) with tertiary phosphanes. They act as [L C −P] + transfer reagents in phospha-Wittig-type reactions, when converted with various thiocarbonyls, giving unprecedented cationic phosphaalkenes [L C −P�CR 2 ] + (5a-f[OTf]) or phosphanides [L C −P−CR(NR 2 ′)] + (6a-d[OTf]). Theoretical calculations suggest that three-membered cyclic thiophosphiranes are crucial intermediates of this reaction. To test this hypothesis, treatment of [L C −P−PPh 3 ] + with phosphaalkenes, that are isolobal to thioketones, permits the isolation of diphosphirane salts 11a,b[OTf]. Furthermore, preliminary studies suggest that the cationic phosphaalkene [L C −P�CPh 2 ] + may be employed to access rare examples of η 2 −P�C π-complexes with Pd 0 and Pt 0 when treated with [Pd(PPh 3 ) 4 ] and [Pt(PPh 3 ) 3 ] for which analogous complexes of neutral phosphaalkenes are scarce. The versatility of [L C −P] +as a valuable P 1 building block was showcased in substitution reactions of the transferred L C -substituent using nucleophiles. This is demonstrated through the reactions of 5a[OTf] and 6c[OTf] with Grignard reagents and KNPh 2 , providing a convenient, highyielding access to MesP�CPh 2 (16) and otherwise difficult-to-synthesize 1,3-diphosphetane 17 and P-aminophosphaalkenes.

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Ein diphos‐Komplex von P^⊕: das 1,1,3,3‐Tetraphenyl‐1λ⁵,2λ³,3λ⁵‐triphospholenyl‐Kation

Cited by 32 publications

References 10 publications

Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands

Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands

Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters

Cationic Phosphinidene as a Versatile P₁ Building Block: [L_C–P]⁺ Transfer from Phosphonio–Phosphanides [L_C–P–PR₃]⁺ and Subsequent L_C Replacement Reactions (L_C = N-Heterocyclic Carbene)

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Ein diphos‐Komplex von P⊕: das 1,1,3,3‐Tetraphenyl‐1λ5,2λ3,3λ5‐triphospholenyl‐Kation

Cited by 32 publications

References 10 publications

Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands

Hypervalent, Low-Coordinate Phosphorus(III) Centers in Complexes of the Phosphadiazonium Cation with Chelate Ligands

Stabilized Arsenic(I) Iodide: A Ready Source of Arsenic Iodide Fragments and a Useful Reagent for the Generation of Clusters

Cationic Phosphinidene as a Versatile P1 Building Block: [LC–P]+ Transfer from Phosphonio–Phosphanides [LC–P–PR3]+ and Subsequent LC Replacement Reactions (LC = N-Heterocyclic Carbene)

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Ein diphos‐Komplex von P^⊕: das 1,1,3,3‐Tetraphenyl‐1λ⁵,2λ³,3λ⁵‐triphospholenyl‐Kation

Cationic Phosphinidene as a Versatile P₁ Building Block: [L_C–P]⁺ Transfer from Phosphonio–Phosphanides [L_C–P–PR₃]⁺ and Subsequent L_C Replacement Reactions (L_C = N-Heterocyclic Carbene)