Erzeugung und Ionisationsmuster der iso(valenz)elektronischen Verbindungen ClP(O)<sub>2</sub> und ClP(S)<sub>2</sub>

Meisel, M.; Bock, Hans; Solouki, Bahman; Kremer, Matthias

doi:10.1002/ange.19891011010

Cited by 25 publications

(4 citation statements)

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“…The relevant N3P bond length of 1.849 (6) A Ê was the longest known at that time. The proposed bonding model corresponds with the thermal behaviour of this type of compound, which has been shown by photoelectron spectroscopic experiments on py3PX 2 Y (X is O or S and Y is F or Cl; Meisel et al, 1989;Bock et al, 1992).…”

Section: Commentsupporting

confidence: 52%

Triorganophosphine–dithiomonometaphosphoryl halides

et al. 2002

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The title compounds, ethyldiphenylphosphine-dithiomonometaphosphoryl chloride, EtPh(2)P-->PS(2)Cl, C(14)H(15)ClP(2)S(2), (I), and tris-n-propylphosphine-dithiomonometaphosphoryl chloride and bromide, nPr(3)P-->PS(2)Cl, C(9)H(21)ClP(2)S(2), (II), and nPr(3)P-->PS(2)Br, C(9)H(21)BrP(2)S(2), (III), respectively, are the first phosphine-stabilized dithiomonometaphosphoryl halides to be structurally characterized. In the tris-n-propylphosphine derivatives, the central P-->P donor-acceptor bond becomes longer in the order bromo < chloro < fluoro. Substitution of the tris-n-propylphosphine group in (II) by the more bulky ethyldiphenylphosphine group also leads to a longer P-->P bond. These structural features agree with the observed 31P NMR data. In (II) and (III), the central P-P bond coincides with the crystallographic threefold axis, entailing site-occupational disorder for the S(2)Y group.

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Section: Commentsupporting

confidence: 52%

Triorganophosphine–dithiomonometaphosphoryl halides

et al. 2002

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“…P 4 O 10 is known to decompose to various activated phosphate species, 47 and to react with pyridine at 70 °C to form bipyridinium phosphates. 46,48 Therefore, a series of further phosphorylating agents were evaluated as potential reactive intermediates (Table S4 and p. S24†). Among them, bipyridinium phosphate P 2 O 5 L 2 (L = pyridine) was found to form PEP in 3% yield after 90 min at 60 °C (Table S4,† entry 9).…”

Section: Resultsmentioning

confidence: 99%

A single phosphorylation mechanism in early metabolism – the case of phosphoenolpyruvate

Zimmermann,

Mayer,

Moran

2023

Chem. Sci.

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“…The formation of a cation [P(O)Cl(L) 4 ] 2+ (L = Lewis base), analogous to the reported [SiCl 2 (NMI) 4 ] 2+ , is thus hindered, and a base-catalyzed dismutation of POCl 3 to PCl 5 and ClPO 2 occurs. The coordinatively unsaturated σ 3 -λ 5 -phosphorane ClPO 2 is ligand-stabilized as the adduct (DMAP)PO 2 Cl, which is then transformed into the [(DMAP) 2 PO 2 ] + cation in its subsequent reaction with another DMAP molecule. The reactions of POBr 3 with pyridines proceed analogously, but besides DMAP also the pyridine exhibits a sufficient Lewis basicity to initiate the dismutation process.…”

Section: Discussionmentioning

confidence: 99%

Base-Induced Dismutation of POCl₃ and POBr₃: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations

et al. 2004

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The interaction between POCl(3) or POBr(3) and pyridine or DMAP has been reinvestigated to clarify the discrepancies between previously published results concerning the Lewis acidity of phosphoryl halides and their behavior toward pyridine bases. The obtained results show that POCl(3) virtually does not react with pyridine, while it does with 4-(dimethylamino)pyridine (DMAP), even in SO(2) solution, to yield an ionic compound [(DMAP)(2)PO(2)]Cl.3SO(2) (1.3SO(2)). Its recrystallization from acetonitrile gives [(DMAP)(2)PO(2)]Cl.CH(3)CN (1.CH(3)CN). The POBr(3) reacts readily with both DMAP and pyridine forming the analogous tribromides, [(DMAP)(2)PO(2)]Br(3) (2) and [(py)(2)PO(2)]Br(3) (3), respectively. Treatment of 3 with Me(3)SiOSO(2)CF(3) in acetonitrile solution led to [(py)(2)PO(2)][CF(3)SO(3)].CH(3)CN (4), while the reaction between 1.CH(3)CN and Me(3)SiOPOF(2) gave [(DMAP)(2)PO(2)][PO(2)F(2)] (5). The crystal structures of 1.CH(3)CN, 1.3SO(2), 2, and 4 revealed that all four compounds are ionic containing the distorted tetrahedral cations [(DMAP)(2)PO(2)](+) and [(py)(2)PO(2)](+). Both ions represent a donor-stabilized form of the so far unknown cation [PO(2)](+). The geometry of [(DMAP)(2)PO(2)](+), optimized by density functional calculations at the B3LYP/6-31G(d,p) level, is in good agreement with X-ray structural data. The NBO analysis of natural atomic charges shows an extensive delocalization of the [PO(2)](+) intrinsic positive charge and indicates a contribution of the electrostatic attraction to the formation of N-P donor-acceptor bonds. According to a (31)P NMR study, the reactions of both phosphoryl halides with DMAP proceed via successive formation of the intermediates [(DMAP)POX(2)](+) and (DMAP)PO(2)X to give an equimolar mixture of [(DMAP)(2)PO(2)](+) and PX(5) (X = Cl, Br) as the end products. The NMR spectroscopic identification of the cations [(DMAP)POX(2)](+) and [(DMAP)(2)PO(2)](+) was supported by ab initio calculations of their chemical shifts.

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Erzeugung und Ionisationsmuster der iso(valenz)elektronischen Verbindungen ClP(O)₂ und ClP(S)₂

Cited by 25 publications

References 28 publications

Triorganophosphine–dithiomonometaphosphoryl halides

Triorganophosphine–dithiomonometaphosphoryl halides

A single phosphorylation mechanism in early metabolism – the case of phosphoenolpyruvate

Base-Induced Dismutation of POCl₃ and POBr₃: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations

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Erzeugung und Ionisationsmuster der iso(valenz)elektronischen Verbindungen ClP(O)2 und ClP(S)2

Cited by 25 publications

References 28 publications

Triorganophosphine–dithiomonometaphosphoryl halides

Triorganophosphine–dithiomonometaphosphoryl halides

A single phosphorylation mechanism in early metabolism – the case of phosphoenolpyruvate

Base-Induced Dismutation of POCl3 and POBr3: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations

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Erzeugung und Ionisationsmuster der iso(valenz)elektronischen Verbindungen ClP(O)₂ und ClP(S)₂

Base-Induced Dismutation of POCl₃ and POBr₃: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations