Structural Alternatives in R<sub>2</sub>(Cl)P:GaCl<sub>3</sub> Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Burford, Neil; Cameron, T. Stanley; LeBlanc, Daren J.; Losier, Pierre; Sereda, and Sergey; Wu, Gang

doi:10.1021/om9703595

Cited by 74 publications

(73 citation statements)

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“…[11] The formation of R 2 P 5 + cages can be rationalized in terms of Equations (A-C) (Scheme 3). However, this is an oversimplified explanation since free phosphenium ions cannot be observed in mixtures of most alkyl-and arylsubstituted chlorophosphanes and GaCl 3 in solution.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of Cationic R₂P₅⁺ Cages and Subsequent Chalcogenation Reactions

Holthausen

Hepp

Weigand

2013

Chemistry A European J

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Cationic R2P5(+) cage compounds (1(+)) have been synthesized by the stoichiometric reaction of R2PCl, GaCl3 and P4. The reaction conditions depend on the substituent R. Alkyl-substituted derivatives (1 a-1 d[GaCl4]) are best synthesized under solvent-free conditions, whereas aryl-substituted derivatives (1 e-1 h[GaCl4]) are formed in C6H5F. All compounds have been prepared on a multi-gram scale in good to excellent yields and have been fully characterized with an emphasis on (31P NMR spectroscopy in solution and single-crystal structure determination. Subsequent chalcogenation reactions of cations R2P5(+) (1 a(+), 1 e(+)) and trication Ph6P7(3+) (3(3+)) with elemental sulfur (α-S8) or grey selenium (Se(grey)) yielded a series of unique polyphosphorus-chalcogen cations (4 a(+), 4 e(+), 5 a(+), 6(2+) and 7(2+)), possessing nortricyclane-type molecular structures. An in-depth study of the (31)P{(1)H} and (77)Se NMR spectroscopic parameters is presented, and correlations between the substitution pattern and the observed structural features have been investigated in detail.

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Section: Resultsmentioning

confidence: 99%

“…The formation of 13 and 14A C H T U N G T R E N N U N G [GaCl 4 ] is observed in solution [11] and in melts. Adduct 13 reacts with R 2 PCl to give the phosphanylphosphonium species 14A C H T U N G T R E N N U N G [GaCl 4 ] according to equilibrium A.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Cationic R₂P₅⁺ Cages and Subsequent Chalcogenation Reactions

Holthausen

Hepp

Weigand

2013

Chemistry A European J

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“…The same questions apply in the metal-P-coordinated series (Scheme 1b). [19] Following pioneering reports of monodentate amidiniophosphine ligands, [20] we recently described the BIMIONAP (BIMIONAP = N-methylated BIMINAP cation, BIMI-NAP = formal contraction of the acronyms BIMIP = 2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole and BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) chelate version 1, combining an amidiniophosphine end with a neutral phosphine end.…”

Section: Introductionmentioning

confidence: 99%

Imidazoliophosphines are True N‐Heterocyclic Carbene (NHC)–Phosphenium Adducts

Abdellah

Lepetit

Canac

et al. 2010

Chemistry A European J

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Whereas the external nucleophilic reactivity of α-amidiniophosphines has been previously illustrated by their complexation to transition-metal centers, their internal electrophilic reactivity is herein investigated by using BIMIONAP (BIMIONAP=N-methylated BIMINAP cation, BIMINAP=formal contraction of the acronyms BIMIP=2,2'-bis(diphenylphosphino)-1,1'-bibenzimidazole and BINAP=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl). Reaction of tetraethylammonium chloride with free BIMIONAP is found to induce heterolytic cleavage of the N(2)C-P bond to give chlorodiphenylphosphine and a transient phosphine-N-heterocyclic carbene (NHC) species that is trapped in situ by protonation to the corresponding phosphine-benzimidazolium cation. When the chloride anion reacts with the cationic [Pd(η(2)-BIMIONAP)Cl(2)] complex, the same cleavage occurs and the phosphine-NHC moiety is trapped in the corresponding [PdCl(2)(η(2)-phosphine-NHC)] complex. When the chloride anion reacts with the dicationic [Pd(π-allyl)(η(2)-BIMIONAP)](+) complex, allyldiphenylphosphine is produced, and the [PdCl(η(2)-phosphine-NHC)(PPh(2)CH(2)CH=CH(2))](+) complex is obtained. Reaction of free BIMIONAP with the harder n-butyllithium nucleophile also induces heterolytic cleavage of the N(2)C-P bond, from which the phosphine-NHC moiety is trapped by hydrolysis of the benzimidazole ring or by P,C-sulfurization. Cleavage of a C-P bond with the weak Cl(-) nucleophile to release the reactive NHC moiety (according to the unusual scheme C-P+Cl(-)→C:+Cl-P) is a definite experimental indication of the dative nature of the N(2)C-P bond of amidiniophosphines, which are, therefore, better described as NHC→phosphenium adducts. This interpretation is supported by the calculation, at the DFT level, of a heterolytic dissociation mode of the N(2)C-P bond lower in energy than the homolytic one. A mesomeric description of the NHC→phosphenium entity is also proposed on the basis of electron localization function (ELF) and atoms in molecules (AIM) analyses. Finally ELF and AIM-based Fukui indices, molecular orbitals, and MESP analyses show that the initial attack of Cl(-) takes place at the carbenic atom of BIMIONAP.

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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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Structural Alternatives in R₂(Cl)P:GaCl₃ Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Cited by 74 publications

References 50 publications

Synthesis of Cationic R₂P₅⁺ Cages and Subsequent Chalcogenation Reactions

Synthesis of Cationic R₂P₅⁺ Cages and Subsequent Chalcogenation Reactions

Imidazoliophosphines are True N‐Heterocyclic Carbene (NHC)–Phosphenium Adducts

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

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Structural Alternatives in R2(Cl)P:GaCl3 Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Cited by 74 publications

References 50 publications

Synthesis of Cationic R2P5+ Cages and Subsequent Chalcogenation Reactions

Synthesis of Cationic R2P5+ Cages and Subsequent Chalcogenation Reactions

Imidazoliophosphines are True N‐Heterocyclic Carbene (NHC)–Phosphenium Adducts

Facile Synthetic Methods for the Diversification of Catena‐Polyphosphorus Cations

Contact Info

Product

Resources

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Structural Alternatives in R₂(Cl)P:GaCl₃ Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P → P Coordination

Synthesis of Cationic R₂P₅⁺ Cages and Subsequent Chalcogenation Reactions

Synthesis of Cationic R₂P₅⁺ Cages and Subsequent Chalcogenation Reactions