Symmetrical and Unsymmetrical Triphosphenium Ions

Schmidpeter, Alfred; Lochschmidt, Siegfried; Sheldrick, William S.

doi:10.1002/anie.198502261

Cited by 97 publications

(76 citation statements)

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“…[2] Anionic variants were first reported by Fluck, [3] and Schmidpeter subsequently developed the first cationic derivatives. [4,5] Since that time, the reactivity of the PPP fragment has been well developed by several groups,i ncluding our own. [6][7][8][9][10][11][12] In spite of typicallyb eing drawn as having two lone pairs on the dicoordinate phosphorus atom (cf.…”

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confidence: 99%

Diphosphoniodiphosphene Formation by Transition Metal Insertion into a Triphosphenium Zwitterion

Kosnik

Binder

Nascimento

et al. 2018

Chemistry A European J

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Treatmento ft wo equivalents of the triphosphenium zwitterion L with sources of Ni 0 and Pd 0 form the mononuclear h 2 -diphosphoniodiphosphene complexes 1 and 2.T he reactionb etween L and [FeCp(CO) 2 ] 2 resultsi n the binuclear m-h 1 :h 1 -diphosphoniodiphosphene iron complex 3,w hich features an alternative bondingm otif of the diphosphoniodiphosphene unit. The formation of these speciesh as been confirmed by spectroscopic methods and single-crystal X-ray diffraction analysis, and their electronic structures have been elucidated using computational methods.Tremendous strides have been made in oligophosphorus chemistry over the past few decades. [1] An importants ubset of mixed coordinateP ÀPb onded compounds are so-called triphosphenium ions (Figure 1). [2] Anionic variants were first reported by Fluck, [3] and Schmidpeter subsequently developed the first cationic derivatives. [4,5] Since that time, the reactivity of the PPP fragment has been well developed by several groups,i ncluding our own. [6][7][8][9][10][11][12] In spite of typicallyb eing drawn as having two lone pairs on the dicoordinate phosphorus atom (cf. phosphanides), triphosphenium cationsa re poor nucleophiles. This observation is exemplified by their inability to form isolable metal complexesa nd it has been rationalized by two factors:t heir overall positive charge, which stabilizes the highest occupied molecular orbital( HOMO), and the strong negative hyperconjugation( p-backbonding) of electron density from the centralp hosphorus atom into the flanking phosphines. [8] To overcome this deficiency,t he Ragogna group designed az witterionic triphosphenium that incorporates a negativelyc harged borate functionality into the backbone. [13,14] Apart from enhancing solubility,t hey demonstrated that this also enhancest he nucleophilicity of the central phosphorus atom and thus they were able to isolatet he first examples of triphosphenium metal complexes.O ur groupp ut forward another design for az witterionic triphosphenium incorporating a cyclopentadienide (Cp) fragment into the backbone. [15] Indeed, we were able to isolate many mono-andb i-metallic complexeso fL (see Figure 1), [16] but we were met with particularly interesting results while investigating L'sc oordinationc hemistry with late transitionm etals.Ta rgeting the complex NiL 2 ,t wo equivalents of L were reacted with one equivalent Ni(COD) 2 .E xamination of the 31 PNMR spectrum of the reactionm ixture gave ar emarkably clean spectrum,w hich featured ac omplex pattern with three second-order multiplets centered at À90.5, 9.5, and 15.3 ppm (Figure 2). The magnetic inequivalence apparent by these signals as well as the introduction of an ew chemically unique phosphorus environment suggested the formation of aP ÀPi nsertionp roduct, which would render the two phosphonio fragmentso ft he triphosphenium chemically inequivalent. Perplexingly,m ass spectrometry performedo nas ample of this product gave am olecular ion peak consistent with the composition NiL 2 ,t hough this speciesc ould ...

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Diphosphoniodiphosphene Formation by Transition Metal Insertion into a Triphosphenium Zwitterion

Kosnik

Binder

Nascimento

et al. 2018

Chemistry A European J

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Small Cyclopolyphosphinophosphonium Cations: Systematic Development of Fundamental catena‐Phosphorus Frameworks

et al. 2005

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Recognizing that catenation of carbon is principally responsible for the diversity and extent of organic chemistry, the "diagonal relationship" between carbon and phosphorus in the Periodic Table is often quoted [1,2] in the discussion of the numerous catenated polyphosphines [2][3][4][5][6] and polyphosphorus anions. [2][3][4][7][8][9][10][11][12] catena-Phosphorus cation systems are less well developed despite the classical chemistry of phosphonium salts, but the pioneering contributions of Schmidpeter and coworkers [13][14][15] and Schmutzler et al. [16] have highlighted new aspects of structure and bonding that prompt the establishment of a comprehensive polyphosphinophosphonium series. Our high-yielding and facile methods for the synthesis of the prototypical phosphinophosphonium 1, [17] diphosphinophosphonium 2, [18] and cyclotetraphosphinophosphonium 5 [18] cations have now been applied to the preparation of the first examples of cyclodiphosphinophosphonium 3 and cyclotriphosphinophosphonium 4 cations (Scheme 1). Isolation of these new frameworks is surprising in light of the exclusive formation of 5 over possible tetra-and hexaphosphorus derivatives with phenyl substituents at the phosphorus centers.[18] Derivatives of 3 and 4 provide representative frameworks that complete a series of the smallest cyclopolyphosphinophosphonium cations 3-5, and their characterization is pivotal in the systematic development of fundamental phosphorus chemistry.31 P NMR spectra of reaction mixtures containing (PtBu) 3 (6 a) with excess MeOTf show quantitative formation of [(PtBu) 3 Me][OTf] (3 a-OTf; Figure 1 a and Scheme 2 a). The spectrum can be approximated as an AMX [19] spin system and is consistent with the solid-state structure of 3 a-OTf (Figure 2 a), thus demonstrating stereoselective methylation of 6 a at either of the syn-configured centers to give a racemic Scheme 1. Prototypical catena-polyphosphinophosphonium cation frameworks. 31 P NMR spectra at 101.3 MHz: a) mixture of MeOTf (2 equiv) and (PtBu) 3 , which shows the approximate AMX pattern of 3 a-OTf; b) mixture of MeOTf (2 equiv) and (PCy) 4 , which shows the approximate A 2 MX pattern of 4 a-OTf; c) experimental (top) and simulated (inverted) AB 2 X pattern of pure 4 b-OTf.

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“…The P-P distances in all four compounds fall within a narrow 2.21-2.24 range, which is consistent with the literature data for a single P À P bond. [35] However, the two P B sites in each of 4, 5, and 7 are distinct: the plane defined by one of the P B atoms (P2) and its attendant aryl ring includes P A (P1), the plane so defined by the other P B (P3) does not. This relates to the inequivalence of the two P B nuclei in the NMR spectra of 5 and 6.…”

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Phosphorus(III) Cations Supported by a PNP Pincer Ligand and Sub‐Stoichiometric Generation of P₄ from Thermolysis of a Nickel Insertion Product

Herbert

Miller

Ozerov

2012

Chemistry A European J

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Neutral, mono-, and dicationic phosphorus(III) compounds are accessible with a supporting PNP pincer ligand (PNP = [4-Me-2-iPr(2)P-C(6)H(3))(2)N]). Reaction of (PNP)H with PCl(3) and nBu(3)N furnished (PNP)PCl(2) (1), which displays a highly temperature-dependent structure in solution. Synthesis and characterization by NMR spectroscopy and X-ray crystallography of Cl/Br-scrambled derivatives, a monocationic derivative [(PNP)PCl][HCB(11)H(11)] (4), and the dicationic derivatives [(PNP)P][OTf](2) (5), [(PNP)P][B(C(6)F(5))(4)](2) (6), [(PNP)P][B(12)Cl(12)] (7) established that 1 not only undergoes several fluxional processes in solution but also possesses a temperature-dependent ground state structure. Reaction of 1 with a Ni(0) source initially leads to a phosphine-phosphinidene complex, followed by thermal generation of P(4).

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Symmetrical and Unsymmetrical Triphosphenium Ions

Cited by 97 publications

References 6 publications

Diphosphoniodiphosphene Formation by Transition Metal Insertion into a Triphosphenium Zwitterion

Diphosphoniodiphosphene Formation by Transition Metal Insertion into a Triphosphenium Zwitterion

Small Cyclopolyphosphinophosphonium Cations: Systematic Development of Fundamental catena‐Phosphorus Frameworks

Phosphorus(III) Cations Supported by a PNP Pincer Ligand and Sub‐Stoichiometric Generation of P₄ from Thermolysis of a Nickel Insertion Product

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Symmetrical and Unsymmetrical Triphosphenium Ions

Cited by 97 publications

References 6 publications

Diphosphoniodiphosphene Formation by Transition Metal Insertion into a Triphosphenium Zwitterion

Diphosphoniodiphosphene Formation by Transition Metal Insertion into a Triphosphenium Zwitterion

Small Cyclopolyphosphinophosphonium Cations: Systematic Development of Fundamental catena‐Phosphorus Frameworks

Phosphorus(III) Cations Supported by a PNP Pincer Ligand and Sub‐Stoichiometric Generation of P4 from Thermolysis of a Nickel Insertion Product

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Phosphorus(III) Cations Supported by a PNP Pincer Ligand and Sub‐Stoichiometric Generation of P₄ from Thermolysis of a Nickel Insertion Product