The chemistry of cationic polyphosphorus cages – syntheses, structure and reactivity

Holthausen, Michael H.; Weigand, Jan J.

doi:10.1039/c4cs00019f

Cited by 83 publications

(38 citation statements)

References 119 publications

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“…After work-up,both compounds can be isolated in 72 %and 85 %yield, respectively.Suitable crystals for X-ray diffraction analyses were obtained by slow diffusion of n-hexane into asaturated CH 2 Cl 2 solution of 4a . Molecular structure of cations 3b + , 4b + ,and 5b + of the respective triflate salts; [33] hydrogen atoms, solvate molecules, and anions are omitted for clarity and ellipsoids are set at 50 %p robability;s elected bond lengths []a nd angles [8 8]: 3b + :P1-N1 1.7334 (11),P 1-N2 1.7007 (11), N5-P1-N31 02.51 (5); 4b + :P1-P2 2.2248(11), P2-P3 2.2181 (11), P1-P2-P39 8.37(4) 5b + :P 1-P2 2.2222(5), P1-P3 2.2311 (5), P2-P1-P31 06.539 (19).…”

Section: Resultsmentioning

confidence: 99%

“…Mechanistically,the formation of 9[OTf] 4 is considered as aP ÀPb ond cleavage reaction of 5b[OTf] by nucleophilic [33] hydrogen atoms, solvate molecules, and anions are omitted for clarity and ellipsoids are set at 50 %p robability;s elected bond lengths []and angles [8 8]: P1-P2 2.2364 (5), P2-P3 2.2345(6), P3-P4 2.2397 (5), P1-P2-P3 94. 33(2), P2-P3-P4 99.47(2).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[1] As shown by the pioneering work of Baudler, [2] von Schnering, [3] Krossing, [4] and numerous other groups,this has resulted in alarge variety of neutral, anionic, and cationic polyphosphanes. [5] Synthetic methods for the preparation of polyphosphanes from P 1 sources are typically based on salt metathesis of ah alophosphane with ametal phosphide, [2,6] the reaction of chlorophosphanes with silyl-or stannylphosphanes, [7] or the reduction of ahalophosphane with alkali metals. [8] Nevertheless,t he established routes towards neutral polyphosphanes are often plagued by poor selectivity and low yields.…”

Section: Introductionmentioning

confidence: 99%

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P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

et al. 2019

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[LCRP((PhP)2C2H4)][OTf] (4 a,b[OTf]) and [LCiPrP(PPh2)2][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [LCRP(pyr)2][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; LCR=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C2H4P(H)Ph) and Ph2PH. A stepwise double P−N/P−P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph2P)2(LCMeP)2][OTf]2 (7 a[OTf]2) is observed when reacting 3 a[OTf] with diphosphane P2Ph4. The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH3CN)4]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2PPLCiPr)Au}4][OTf]4 (9[OTf]4) was unexpectedly formed as a result of a chloride‐induced P−P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH3CN)3][OTf]2 (M=Cu, Ag) (10[OTf]2, 11[OTf]2).

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Section: Resultsmentioning

confidence: 99%

Section: Angewandte Chemiementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

et al. 2019

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“…[2] In general, the chemistry of the polysulfides,a sw ell as their coordination chemistry,h as been investigated intensively. [4] Anumber of molecular polypnictide Zintl anions such as E 8 4À (E = P, As,Sb) have been obtained from the elements or other precursors. [4] Anumber of molecular polypnictide Zintl anions such as E 8 4À (E = P, As,Sb) have been obtained from the elements or other precursors.…”

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confidence: 99%

Polysulfide Coordination Clusters of the Lanthanides

Bestgen

Gamer

et al. 2017

Angew Chem Int Ed

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The reaction of [(DippForm) Ln(thf) ] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm) Ln S ] (Ln=Sm, Yb; DippForm=N,N'-bis(2,6-diisopropylphenyl)formamidinate). These are the first f element coordination clusters (Ln S ) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S with divalent lanthanides.

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“…20 Otherwise, the P 4 activation has been performed in the presence of carbene moieties, which afford partial but incomplete P-P demolition and formation of the PvP double bond. 21 The latter feature has never been observed by us, excluding such a possibility in our mechanism (vide infra).…”

Section: Introductionmentioning

confidence: 99%

The atomic level mechanism of white phosphorous demolition by di-iodine

et al. 2018

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A detailed mechanism of the I 2 -induced transformation of white phosphorus into PI 3 emerges from a DFT analysis. This multi-step process implies that at any stage one P-P and two I-I bonds cleavages, associated with the formation of two P-I bonds plus an in situ generated brand new I 2 molecule.Significant electron transfer between the atoms is observed at any step, but the reactions are better defined as concerted rather than redox. Along the steepest descent to the product, no significant barrier is encountered except for the very first P 4 activation, which costs +14.6 kcal mol −1 . At the atomic level, one first I 2 molecule, a typical mild oxidant, is first involved in a linear halogen bonding interaction (XB) with one P donor, while its terminal I atom is engaged in an additional XB adduct with a second I 2 .Significant electron transfer through the combined diatomics allows the external I atom of the dangling I 3 grouping to convey electrons into the σ* level of one P-P bond with its consequent cleavage. This implies at some point the appearance of a six-membered ring, which alternatively switches its bonding and no-bonding interactions. The final transformation of the P 2 I 4 diphosphine into two PI 3 phosphines is enlightening also for the specific role of the I substituents. In fact, it is proved that an organo-diphosphine analogue hardly undergoes the separation of two phosphines, as reported in the literature. This is attributable to the particularly high donor power of the carbo-substituted P atoms, which prevents the concertedness of the reaction but favors charge separation in an unreactive ion pair.

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The chemistry of cationic polyphosphorus cages – syntheses, structure and reactivity

Abstract: The aim of this review is to provide a comprehensive view of the chemistry of cationic polyphosphorus cages.

Cited by 83 publications

References 119 publications

P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

Polysulfide Coordination Clusters of the Lanthanides

The atomic level mechanism of white phosphorous demolition by di-iodine

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