Neue Produkte aus PCl3, P(NMe2)3 und AlCl3

Schmidpeter, Alfred; Lochschmidt, Siegfried

doi:10.1002/ange.19860980320

Cited by 24 publications

(10 citation statements)

References 9 publications

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confidence: 99%

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

Burford¹,

Dyker²,

Decken³

2005

Angew Chem Int Ed

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The propensity for phosphorus to form catenated compounds is evidenced by the extensive arrays of structurally characterized polyphosphines [1,2] and homopolyatomic anions reported. [3] In contrast, comprehensively characterized polyphosphorus cations are limited to phosphinophosphonium 1, [4][5][6][7][8][9] phosphinodiphosphonium 2, [10] diphosphiranodiphosphonium 3, [11] and phosphidodiphosphonium 4 [12,13] ions (Scheme 1). Nevertheless, recent and unique examples of cations 5, [7,14] 6, [15] 7, [8,14,16] and 8 [17] illustrate the potential for diversification and highlight catena-polyphosphorus cations as an underexplored avenue in phosphorus chemistry. In this context, we have exploited facile reactions of polyphosphines (di, tetra, and penta species) to prepare a series of new organosubstituted diphosphinophosphonium 9 and cyclotetraphosphinophosphonium cations 10.The 31 P NMR spectra for reaction mixtures of tetramethyldiphosphane or tetraphenyldiphosphane with Me 2 PCl or Ph 2 PCl in the presence of Me 3 SiOSO 2 CF 3 (TMSOTf) [18] show rapid, quantitative formation of the corresponding organosubstituted catena-diphosphanophosphonium cations 9 a, 9 b, 9 c, and 9 f (Scheme 2). Derivatives of 9 can be envisaged as diphosphine ligands on phosphenium Lewis acceptors (analogous to 1, thus representing complexes of R 3 P on R 0 2 P + ), [7] and are structural isomers of 4.[12] Cation 9 f is a rearrangement product of 9 d or the product of Me 2 P + insertion into the PÀP bond of Ph 2 PÀPPh 2 . The formation of derivative 9 e was not observed. The preferred formation of 9 f over 9 d and 9 c over 9 e is likely to be a result of the steric interactions between the substituents and the relative donor (PMe 2 versus PPh 2 )/acceptor (PMe 2 + versus PPh 2 + ) properties of the PR 2 units.An unusual eclipsed/staggered (C s ) conformation is observed for the cation of 9 a-OTf (OTf = trifluoromethanesulfonate) in the solid state (Figure 1). Retention of this nonsymmetric arrangement in solution is evidenced by the slight nonequivalence (Dd < 0.1 ppm, DJ = 11-35 Hz) of the terminal phosphorus centers in the 31 P NMR spectra of 9 a, 9 b, and 9 f at 193 K (Table 1; Figure 2 shows the 31 P NMR spectrum of 9 b-OTf as an example). The 31 P NMR spectra of all derivatives of 9 at RT show broad, poorly defined triplets and doublets, thus indicating dynamic behavior that may enable rearrangement of 9 d to 9 f by dissociation to Ph 2 PÀ PMe 2 and Ph 2 P + (Scheme 2).Scheme 1. Previously characterized polyphosphorus cations. c = alkyl or aryl substituent; R = 2,6-(OMe) 2 C 6 H 3 .

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confidence: 99%

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

Burford¹,

Dyker²,

Decken³

2005

Angew Chem Int Ed

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“…[13a,b, 20,21] An indication of the extraordinary reactions that may be possible with these trapped monoatomic electrophiles is furnished by the report from Driess et al on the synthesis of the intriguing square-planar phosphonium cation P[Zr(H)Cp 2 ] 4 + , where the dicoordinate P-centred cation [(Me 2 N) 3 P] 2 P + was used as a source of "P + " in the reaction with [Cp 2 Zr(H)Cl]. [22] To date, the reactions of the novel chalcogenium dications in salts of type 1 and 2 have been limited to a preliminary report of the facile extrusion of the chalcogen from the heterocyclic ring by phosphines to give SPR 3 .…”

Section: Methodsmentioning

confidence: 99%

Ligand‐Stabilized Chalcogen Dications

Chivers

Konu

2009

Angew Chem Int Ed

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Chalcogen-transfer reagents? The bonding in the dicationic rings C(2)N(2)E(2+) (see picture) differs from that in N-heterocyclic carbenes and their isovalent p-block analogues in accommodating a lone pair of electrons with pi symmetry, as well as sigma symmetry, on the chalcogen center. The labile electrophilic chalcogenium dications (E(2+)) are potentially versatile chalcogen-transfer reagents in reactions with a variety of inorganic and organic substrates.

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“…Alkylation gave dications of triphosphines [141] and of tetraphosphines 54 [142]. The hexakis(dimethylamino) triphosphenium ion 55 proved to be particularly useful as a source of P ‫ם‬ [143,144]. Recently, a planar phosphonium derivative has been made from it [145].…”

Section: Alfred Schmidpetermentioning

confidence: 99%