Isolable Phosphanylidene Phosphorane with a Sterically Accessible Two‐Coordinate Phosphorus Atom

Surgenor, Brian A.; Bühl, Michæl; Slawin, Alexandra M. Z.; Woollins, J. Derek; Kilián, Petr

doi:10.1002/anie.201204998

Cited by 77 publications

(64 citation statements)

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“…[17,18] The ease of synthesising the valuable precursor 5,6-dibromoacenaphthene [20] compared to the more laborious method for preparing the naphthalene equivalent, [21] has seen an increasing rise in the use of the acenaphthene scaffold for preparing peri-substituted species. [22][23][24][25][26][27] The related acenaphthylene backbone incorporating a C=C double bond on the bridging moiety, however, has seen limited use. Herein, we report the synthesis and structural characterisation of a series of halogen and chalcogen peri-substituted acenaphthylenes 1-12, analogues of previously reported naphthalenes N1-N12 [18] and acenaphthenes A1-A12, [17] along with 5,6-dihaloacenaphthylenes 13 (Br) [28,29] and 14 (I).…”

Section: ]mentioning

confidence: 99%

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

et al. 2014

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Keywords: acenaphthylene /peri-substitution /3c-4e interaction /X-ray crystallography / DFT calculations/non-covalent A series of peri-substituted acenaphthylenes containing mixed halogen-chalcogen functionalities at the 5,6-positions in 1-6 (Acenapyl [X][EPh] (Acenap = acenaphthylene-5,6-diyl; X = Br, I; E = S, Se, Te) and chalcogen-chalcogen moieties in 7-11 (Acenap [EPh][E`Ph] (Acenap = acenaphthene-5,6-diyl; E/E` = S, Se, Te), have been prepared from their corresponding acenaphthene analogues A1-A11, utilizing 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) for the dehydrogenation of the ethane backbone. The related dihalide compounds 13 and 14 Acenapyl[XX`] (XX` = BrBr, II) have also been prepared following a similar procedure and 1,2,5,6-tetrabromo-1,2-dihydroacenaphthylene A0 was prepared as an intermediate following an alternative route to 13. The series of acenaphthylene compounds have remarkably similar molecular structures to their acenaphthene counterparts, exhibiting an expected increase in periseparation as heavier congeners occupy the close peri-positions.The presence of the ethene bridge, however, naturally compresses the nearest bay angle whilst increasing the splay of the exocyclic peri-atoms, resulting in a minor increase in separation compared with equivalent acenaphthenes. The structures of 1-11, 13 and 14 are discussed and compared with previously reported analogous naphthalene and acenaphthene compounds. Similar to acenaphthene derivatives, aromatic ring conformations and the location of p-type lone-pairs influences the geometry of the peri-region. Under appropriate geometric conditions quasi-linear three-body C Ph -E···Z (E = Te, Se, S; Z = Br/E) fragments provide an attractive component for the E···Z interaction. DFT studies confirm the onset of formation of threecenter, four-electron bonding, similar in extent as observed in analogous acenaphthenes, despite an increase in the peridistances. IntroductionUnderstanding how atoms interact in different bonding situations and the ability to quantify the extent of bonding between two atoms is an ongoing challenge for chemists, and one which dates back to the origins of the electronic theory of valence proposed by Lewis and Langmuir in the early 1900s. [1,2] The stability of molecules was originally ascribed to their ability to pair valence electrons off in chemical bonds to achieve 'stable octets', with the concept of covalence introduced as 'the number of pairs of electrons an atom can share with its neighbor'. [1][2][3] Ambiguity over the bonding in molecules of heavier main-block elements (period 3 and higher), in which an 'octet expansion' would be required in order to conform to conventional Lewis 2c-2e covalent bonding theory, was thus rationalized by the availability of unfilled low-lying d-orbitals. [1] Langmuir, however, accounted for the legitimacy of the octet rule by suggesting the bonding in these species, termed hypervalent, [4] was now ionic rather than covalent in nature. [2] The advancement of molecular orbital theory in t...

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Section: ]mentioning

confidence: 99%

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

et al. 2014

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“…[21][22][23] These compounds display exceptional thermal stability which, in contrast to previous examples, stems from peri-substitution stabilisation. The pnictogen centres were mounted on a rigid acenaphthene backbone, which forces the phosphine moiety into close proximity with the phosphinidene/arsinidene group.…”

Section: Introductionmentioning

confidence: 91%

“…1 H, 13 C{ 1 H}, 31 P and 31 P{ 1 H} NMR spectra were in good agreement with previously published data. [21] Full NMR assignments for this compound can be found in the SI.…”

Section: Acenap(pipr2)(p) 3bmentioning

confidence: 99%

“…Compound 3a was obtained via a dehydrogenation reaction of the primary arsine 1a [23] while 3b was synthesised by deprotection of an intermediate bis(borane) adduct (Scheme 1). [21] To test the plausibility of this mechanism, we decided to mimic this pathway chemically. To this end, we treated the primary arsine with the hydride abstractor triphenylcarbonium tetrafluoroborate (Ph 3 C·BF 4 ), which yielded an isolable arsino-phosphonium salt 2a (Scheme 3).…”

Section: Introductionmentioning

confidence: 99%

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Hydride Abstraction and Deprotonation – an Efficient Route to Low Coordinate Phosphorus and Arsenic Species

et al. 2015

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Treatment of Acenap(PiPr 2 )(EH 2 ) (Acenap = acenaphthene-5,6-diyl; 1a, E = As; 1b, E = P) with Ph 3 C·BF 4 resulted in hydride abstraction to give [Acenap(PiPr 2 )(EH)][BF 4 ] (2a, E = As; 2b, E = P). These represent the first structurally characterised phosphino/arsino-phosphonium salts with secondary arsine/phosphine groups, as well as the first example of a Lewis base stabilised primary arsenium cation. Compounds 2a and 2b were deprotonated with NaH to afford low co-ordinate species Acenap(PiPr 2 )(E) (3a, E = As; 3b, E = P). This provides an alternative and practical synthetic pathway to the phosphanylidene-σ 4 -phosphorane 3b and provides mechanistic insight into the formation of arsanylidene-σ 4 -phosphorane 3a, indirectly supporting the hypothesis that the previously reported dehydrogenation of 1a occurs via an ionic mechanism.

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“…There are some nice examples in the literature where neutral dicoordinate phosphorus compounds are shown to coordinate to two Lewis acids simultaneously. [26][27][28] The most general are compounds H and I prepared by Stalke, which have been shown to act as a four-electron -type donor to tungsten, manganese, and caesium. 29,30 These interesting proligands have also been characterized by charge density studies, which show the presence of two basins of electron density on phosphorus, consistent with "lone pairs" of electrons.…”

Section: Introductionmentioning

confidence: 99%

Utilizing a zwitterionic approach for the synthesis of late transition metal – triphosphenium ion coordination compounds

et al. 2015

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Zwitterionic dicoordinate phosphorus(I) compounds (1 and 2), formally a charge neutral triphosphenium ion or phosphanide, are shown to coordinate to a variety of late transition metals. The reaction of the phosphanide proligands with {Rh(COD)Cl} 2 results in an equilibrium process that varies as a function of temperature or reaction stoichiometry. Palladium(II) compounds have a tendency to chlorinate the borate backbone while giving dimeric coordination compounds (1Pd) and also a decomposition product (3) where the P(I) atom was replaced. Both "lone pairs" of electrons on phosphorus are utilized simultaneously in the dominant product from the reaction of 1 and [PtMe 2 (-SMe 2 )] 2 , while each platinum center ortho-metallated a phenyl substituent on the flanking phosphorus atoms (1Pt). Stable, isolable, and fully characterized dimeric mercury complexes (1Hg and 2Hg) are produced nearly quantitatively from the reaction of the phosphanide proligand with HgCl 2 . All compounds described were structurally characterized using single crystal X-ray diffraction and represent a growing series of zwitterionic P(I) coordination compounds that cannot be isolated when a cationic triphosphenium ion is used. Résumé :Les composés zwitterioniques bis-coordonnés de phosphore(I) (1 et 2), qui sont en fait des ions triphosphénium neutres ou des phosphanures, se sont révélés capables de se coordonner à divers métaux de transition de fin de série. La réaction des proligands phosphanures avec le complexe [Rh(COD)Cl] 2 entraîne un processus d'équilibre qui varie en fonction de la tempéra-ture ou de la stoechiométrie de la réaction. Les composés de palladium(II) ont tendance à chlorer la chaîne principale boratée et à donner, pour leur part, les composés de coordination dimériques (1Pd) ainsi que le produit de décomposition (3) dans lequel l'atome de P(I) a été remplacé. Les deux doublets non liants des électrons du phosphore sont engagés simultanément dans le produit majoritaire provenant de la réaction entre le composé 1 et le complexe [PtMe 2 (-SMe 2 )] 2 . Quant aux noyaux de platine, chacun d'eux s'est inséré en position ortho de l'un des substituants phényles de l'atome de phosphore voisin (1Pt). Des complexes dimériques de mercure (1Hg et 2Hg) stables, isolables et entièrement caractérisés sont produits de façon quasi quantitative par la réaction du proligand phosphanure avec le HgCl 2 . Tous les composés décrits ont été structurellement caractérisés par diffraction des rayons X d'un cristal unique et représentent une série en expansion de composés zwitterioniques de coordination P(I) ne pouvant pas être isolés lorsqu'un cation triphosphénium est utilisé. [Traduit par la Rédaction] Mots-clés : phosphore, zwitterions, chimie de coordination, chimie des éléments du groupe principal.

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Isolable Phosphanylidene Phosphorane with a Sterically Accessible Two‐Coordinate Phosphorus Atom

Abstract: 'P' undressed: A stable phosphanylidene phosphorane with a sterically accessible (naked) two‐coordinate P is reported (see structure). Coordination to Pd0 reveals its phosphine donor/phosphinidene acceptor (R3P→PR′) nature by exposing its phosphinidene‐like reactivity.

Cited by 77 publications

References 30 publications

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

Hydride Abstraction and Deprotonation – an Efficient Route to Low Coordinate Phosphorus and Arsenic Species

Utilizing a zwitterionic approach for the synthesis of late transition metal – triphosphenium ion coordination compounds

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