Beiträge zur Chemie des Phosphors, 76<sup>1</sup> Tricyclohexyl-cyclotriphosphan, Pentacyclohexyl-cyclopentaphosphan und 1.2.3.4-Tetracyclohexyl-cyclo-5-carba-1.2.3.4-tetraphosphan / Contributions to the Chemistry of Phosphorus, 76<sup>1</sup>&lt;br /&gt;Tricyclohexyl-cyclotriphosphane, Pentacyclohexyl-cyclopentaphosphane, and 1,2,3,4-Tetracyclohexyl-cyclo-5-carba-1,2,3,4-tetraphosphane

Baudler, M.; Pinner, C.; Gruner, Christian; Hellmann, J.; Schwamborn, Michael; Kloth, B.

doi:10.1515/znb-1977-1106

Cited by 30 publications

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“…[27] In addition, two new doublets (d = 15.4 and À38.2 ppm, 1 J(P-P) = 295 Hz) are assigned to the new phosphinophosphonium cation in [Me 3 P-PMeCy][OTf] (1 a-OTf), and a low-intensity sharp signal at d = À67 ppm is assigned to 7 (Scheme 3). The abstraction of MeCyP + from 4 a by PMe 3 effects a ring contraction and, in conjunction with a previous methylation step, highlights a synthetically viable transformation from cyclotetraphosphine (PR) 4 to cyclotriphosphine (PR) 3 .…”

Section: Angewandte Chemiementioning

confidence: 99%

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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Section: Angewandte Chemiementioning

confidence: 99%

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

et al. 2005

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“…The thus formed tetraphosphane 23 is, as expected, unstable and rearranges to the isotetraphosphane 24.175 The reaction of (PCF3)4 with fluoroalkyl iodides Rfl has been investigated in detail. 176 23 (34) The action of sulfur on monocyclophosphanes does not only result in cyclophosphane monosulfides with exocyclic bonded sulfur (section II.D.l). On the contrary, an extensive insertion of the sulfur into the P" ring with formation of phosphorus-sulfur heterocycles takes place.…”

Section: Reactions With Ring Cleavagementioning

confidence: 99%

“…The chemistry of 34 is characterized both by analogies with and by differences to the chemistry of the C5H5ion. Thus, 34 reacts with alkyl halides to form, above all, P7R3 and P9R3. The nonaromatic primary product 37 is apparently so unstable that it rearranges spontaneously into the thermodynamically more favored alkylpolyphosphanes.…”

Section: Reactions With Ring Cleavagementioning

confidence: 99%

“…and AB2 spin systems, respectively, observed at low field in the 31P{1H}-NMR spectrum and on the splitting observed under 1H coupling conditions.208'223 A constitutional isomer of the ring system 36 exists in the compound lithium 3,5-di(fert-butyl)-l,2,4-triphosphacyclopentadienide*3DME. 224 The concomitant, spontaneous formation and remarkable thermal stabilities of [34][35][36] reflect the significant stability of anionic, P-containing five-membered rings with delocalized 67r-electron systems.…”

Section: Reactions With Ring Cleavagementioning

confidence: 99%

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Contributions to the chemistry of phosphorus. 218. Monocyclic and polycyclic phosphines

Baudler¹,

Glinka²

1993

Chem. Rev.

317

282

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“…In a preliminary study of reactivity, reaction mixtures that contain 4 a ‐OTf and PMe 3 show the characteristic A 2 B pattern of (PCy) 3 ( 6 c ) in the 31 P NMR spectra 27. In addition, two new doublets ( δ =15.4 and −38.2 ppm, 1 J (P‐P)=295 Hz) are assigned to the new phosphinophosphonium cation in [Me 3 P‐PMeCy][OTf] ( 1 a ‐OTf), and a low‐intensity sharp signal at δ =−67 ppm is assigned to 7 (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Reversible Coordination of Dioxygen by Tripodal Tetraamine Copper Complexes Incorporated in a Porous Silica Framework

Suspène

Brandès

Guilard

2010

Chemistry A European J

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The present study reports the synthesis and rational design of porous structured materials by using a templating method. A tetraethoxysilylated tripodal tetraamine (TREN) was covalently incorporated in a silica framework with a double imprint: A surfactant template and a metal ion imprint. The presence of a cationic surfactant (CTAB) endowed the material with a high porosity, and the tripodal or square-pyramidal topology of the ligand was preserved thanks to the use of the silylated Cu(II) complex. After removal of the surfactant and de-metalation, the incorporated tetraamine was quantitatively complexed by CuCl(2) and the material has shown after thermal activation that a reversible binding of O(2) on the metal ions occurred. This chemisorption process was monitored by UV/Vis and EPR spectroscopies, and the Cu:O(2) adduct was postulated to be an end-on mu-eta(1):eta(1)-peroxodicopper(II) complex bridged by a chloride ion. The Cu(I)-active species, formed during the activation step, were fully recovered during several O(2) binding cycles. The high reactivity of the copper complexes and the room-temperature stability of the dioxygen adduct were explained by the fine adaptability of the tripodal ligand to different geometries, the confinement of the active sites in the hybrid silica that protect them from degradation by a control of the metal-ion microenvironment, as well as the short-range lamellar order of the copper complexes in the framework.

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Abstract: Tricyclohexyl-cyclotriphosphane, (c-C6H11P)3 (1), is another relatively stable compound with a three membered phosphorus ring. It is produced in the reactions of (a) K2(c-C6H11P)4 with CH2Cl2, (b) K2(c-C6H11P)4 with CS2 Show more

Cited by 30 publications

References 0 publications

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

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

Contributions to the chemistry of phosphorus. 218. Monocyclic and polycyclic phosphines

Reversible Coordination of Dioxygen by Tripodal Tetraamine Copper Complexes Incorporated in a Porous Silica Framework

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