Structure of [2((CH3)2N)2PCl].AlCl3, ((CH3)2N)3P.((CH3)2N)2PCl.AlCl3, and related species-diphosphorus cations

Schultz, C. W.; Parry, R. W.

doi:10.1021/ic50166a022

Cited by 72 publications

(87 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Although complicated, the 31 P NMR solution spectra for the derivatives of 10 exhibit a low-field tripletlike signal that is assigned to a phosphonium center and is distinct from a multiplet that corresponds to the four phosphine centers (Figure 3 a, b). The exclusive formation of 10 a and 10 b from either (PhP) 4 or (PhP) 5 demonstrates a thermodynamic preference for the five-membered framework over the hexaphosphorus or pentaphosphorus alternatives 11 and 12 (Scheme 3) and is consistent with the prominence of the cyclopentaphosphorus unit in Hittorfs phosphorus, [19] polyphosphines, and polyphosphorus anions. [3] Pentaphosphorus cations of type 10 were first proposed on the basis of elemental analysis data for the alkylation products of cyclopentaphosphines.…”

supporting

confidence: 54%

“…[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.…”

mentioning

confidence: 99%

“…The 31 P NMR spectra for equimolar mixtures of R 2 PCl and TMSOTf with (PhP) 4 or (PhP) 5 [Eqs. (1) and (2); (Figure 3).…”

mentioning

confidence: 99%

See 2 more Smart Citations

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

Burford¹,

Dyker²,

Decken³

2005

Angew Chem Int Ed

View full text Add to dashboard Cite

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 .

show abstract

supporting

confidence: 54%

mentioning

confidence: 99%

See 1 more Smart Citation

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

Burford¹,

Dyker²,

Decken³

2005

Angew Chem Int Ed

View full text Add to dashboard Cite

show abstract

“…We found that the sequence in which the reactants are added determines the products of the reaction: If a I :3 mixture of PC1, and P(NMe2), in CH2C12 is initially prepared, so that the substituent-exchange reaction (1) can occur, then the subsequently added AICI, reacts according to reactions (2) to (4). The reactions are reversible and, as expected from the stoichiometry, reaction (2) becomes predominant with increasing amounts of AICI,; when AlC13 : PCI, is 4 : 1, it is virtually the only reaction.…”

mentioning

confidence: 99%

“…ref. [2]) and subsequently treated with PCI,, then reductive formation of 5 takes place according to reaction (5).…”

mentioning

confidence: 99%

New Products from PCl₃, P(NMe₂)₃, and AlCl₃

Schmidpeter¹,

Lochschmidt²

1986

Angew. Chem. Int. Ed. Engl.

View full text Add to dashboard Cite

Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphines with Organoelement Chlorides involving Phosphorus, Sulfur, and Selenium; Formation of Stable Phosphino-, Thio-, and Selenophosphonium Salts

Münchenberg

Böge

Thönnessen

et al. 1998

Z. anorg. allg. Chem.

View full text Add to dashboard Cite

Structure of [2((CH3)2N)2PCl].AlCl3, ((CH3)2N)3P.((CH3)2N)2PCl.AlCl3, and related species-diphosphorus cations

Abstract: AlCl3, ((CH3),N)3P ‐ ((CH3)2N),PCl‐AlCl3, and Related Species‐Diphosphorus Cations.

Cited by 72 publications

References 0 publications

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

New Products from PCl₃, P(NMe₂)₃, and AlCl₃

Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphines with Organoelement Chlorides involving Phosphorus, Sulfur, and Selenium; Formation of Stable Phosphino-, Thio-, and Selenophosphonium Salts

Contact Info

Product

Resources

About

Structure of [2((CH3)2N)2PCl].AlCl3, ((CH3)2N)3P.((CH3)2N)2PCl.AlCl3, and related species-diphosphorus cations

Abstract: AlCl3, ((CH3),N)3P ‐ ((CH3)2N),PCl‐AlCl3, and Related Species‐Diphosphorus Cations.

Cited by 72 publications

References 0 publications

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

New Products from PCl3, P(NMe2)3, and AlCl3

Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphines with Organoelement Chlorides involving Phosphorus, Sulfur, and Selenium; Formation of Stable Phosphino-, Thio-, and Selenophosphonium Salts

Contact Info

Product

Resources

About

New Products from PCl₃, P(NMe₂)₃, and AlCl₃