Phosphorus-phosphorus bond. I. Complexes containing highly connected phosphorus atoms, HnMe3-nPPF5. Directly bonded phosphorus-phosphorus coupling constant

Rudolph, R. W.; Schultz, C. W.

doi:10.1021/ja00737a011

Cited by 27 publications

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“…The 31 P{ 1 H} NMR spectrum exhibits a high-frequency doublet of quintets due to PMe 3 and, at low frequency, a doublet of doublets of quintets, due to the phosphorus of the PF 5 unit (Figure c,d and Figures S6 and S7) . The spectrum is in good agreement with the data reported in CH 3 CN solution at 310 K.…”

Section: Resultsmentioning

confidence: 72%

“…Complexes with the heavier and softer donors of group 15 have received little study, apart from the [PF 5 (PMe 3– x H x )] ( x = 0, 1, 2), for which NMR spectroscopic data have been reported. , In fact, pnictine complexes of any p-block fluorides are rare . Phosphine complexes of the types [BF 3 (PR 3 )] (R = alkyl), [F 3 B{μ-R 2 P(CH 2 ) 2 PR 2 }BF 3 ], and [BF 2 { o -C 6 H 4 (PMe 2 ) 2 }] + have recently been reported, along with a limited number of less stable arsine analogues .…”

Section: Introductionmentioning

confidence: 98%

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Tertiary Phosphine and Arsine Complexes of Phosphorus Pentafluoride: Synthesis, Properties, and Electronic Structures

et al. 2020

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The reaction of PMe3 or PPh3 with PF5 in anhydrous CH2Cl2 or hexane forms the white, moisture-sensitive complexes [PF5(PR3)] (R = Me, Ph). Similar reactions involving the diphosphines o-C6H4(PR2)2 afford the complexes [PF4{o-C6H4(PR2)2}][PF6]. The X-ray structures of [PF5(PR3)] and [PF4{o-C6H4(PMe2)2}][PF6] show pseudo-octahedral fluorophosphorus centers. Multinuclear NMR spectra (1H, 19F{1H}, 31P{1H}) show that in solution in CH2Cl2/CD2Cl2 the structures determined crystallographically are the only species present for [PF5(PMe3)] and [PF4{o-C6H4(PMe2)2}][PF6] but that [PF5(PPh3)] and [PF4{o-C6H4(PPh2)2}][PF6] exhibit reversible dissociation of the phosphine at ambient temperatures, although exchange slows at low temperatures. The complex 19F{1H} and 31P{1H} NMR spectra have been analyzed, including those of the cation [PF4{o-C6H4(PMe2)2}]+, which is a second-order AA′XX′B2M spin system. The unstable [PF5(AsMe3)], which decomposes in a few hours at ambient temperatures, has also been isolated and spectroscopically characterized; neither AsPh3 nor SbEt3 forms similar complexes. The electronic structures of the PF5 complexes have been explored by DFT calculations. The DFT optimized geometries for [PF5(PMe3)], [PF5(PPh3)], and [PF4{o-C6H4(PMe2)2}]+ are in good agreement with their respective crystal structure geometries. DFT calculations on the PF5-L complexes reveal the P–L bond strength falls with L in the order PMe3 > PPh3 > AsMe3, consistent with the experimentally observed stabilities, and in the PF5-L complexes, electron transfer from L to PF5 on forming these complexes also follows the order PMe3 > PPh3 ≈ AsMe3.

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Section: Resultsmentioning

confidence: 72%

Section: Introductionmentioning

confidence: 98%

Tertiary Phosphine and Arsine Complexes of Phosphorus Pentafluoride: Synthesis, Properties, and Electronic Structures

et al. 2020

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Eine kationische, makrocyclische Phosphor(V)-Verbindung mit einer linearen PIII-PV-PIII-Kette und sechsfach koordiniertem Phosphor(V)

1998

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Von 1σ⁴, 2σ²‐ zu 1σ⁴, 2σⁿ‐Diphospheten (n = 3–6): die überraschende Beständigkeit der P‐P‐Bindung

et al. 1996

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Phosphorus-phosphorus bond. I. Complexes containing highly connected phosphorus atoms, HnMe3-nPPF5. Directly bonded phosphorus-phosphorus coupling constant

Cited by 27 publications

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Tertiary Phosphine and Arsine Complexes of Phosphorus Pentafluoride: Synthesis, Properties, and Electronic Structures

Tertiary Phosphine and Arsine Complexes of Phosphorus Pentafluoride: Synthesis, Properties, and Electronic Structures

Eine kationische, makrocyclische Phosphor(V)-Verbindung mit einer linearen PIII-PV-PIII-Kette und sechsfach koordiniertem Phosphor(V)

Von 1σ⁴, 2σ²‐ zu 1σ⁴, 2σⁿ‐Diphospheten (n = 3–6): die überraschende Beständigkeit der P‐P‐Bindung

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Phosphorus-phosphorus bond. I. Complexes containing highly connected phosphorus atoms, HnMe3-nPPF5. Directly bonded phosphorus-phosphorus coupling constant

Cited by 27 publications

References 0 publications

Tertiary Phosphine and Arsine Complexes of Phosphorus Pentafluoride: Synthesis, Properties, and Electronic Structures

Tertiary Phosphine and Arsine Complexes of Phosphorus Pentafluoride: Synthesis, Properties, and Electronic Structures

Eine kationische, makrocyclische Phosphor(V)-Verbindung mit einer linearen PIII-PV-PIII-Kette und sechsfach koordiniertem Phosphor(V)

Von 1σ4, 2σ2‐ zu 1σ4, 2σn‐Diphospheten (n = 3–6): die überraschende Beständigkeit der P‐P‐Bindung

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Von 1σ⁴, 2σ²‐ zu 1σ⁴, 2σⁿ‐Diphospheten (n = 3–6): die überraschende Beständigkeit der P‐P‐Bindung