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Gudat, Dietrich; Häp, Stefan; Bajorat, Volker; Nieger, Martin

doi:10.1002/1521-3749(200106)627:6<1119::aid-zaac1119>3.3.co;2-x

Cited by 13 publications

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“…Having shown that quaternisation of the phosphane functionality in 3 with alkyl halides provides easy access to various side-chain-functionalised bis(phosphonio)benzo[c]-phospholide cations, [6] we anticipated that this compound should similarly undergo other typical phosphane reactions such as oxidation or formation of adducts with Lewis acids. In agreement with this assumption, treatment of 2 with equimolar amounts of boraneϪTHF or sulfur afforded quantitative yields (based on 31 P NMR spectroscopic investigation of the reaction mixtures) of the corresponding borane adduct 6 and thioxophosphorane 7, respectively.…”

Section: Syntheses and Spectroscopic Investigationsmentioning

confidence: 99%

“…[8] ); the atom numbering scheme is identical to the one given in Figure 1 . This effect is not observed in 1 and 5, which have identical substituents at the C1 and C3 atoms, and in ''asymmetric'' bis(phosphonio)benzophospholides [6] with two different phosphonio groups. No similar asymmetry of the CϪC bonds on opposite sides of the ring system is observed in any compound.…”

Section: Crystal Structure Studiesmentioning

confidence: 99%

“…This is in agreement with the experimentally observed conformations of 3, 6, 7 and implies a molecular C 1 symmetry. The molecular structures of 1-H and 4-H display C 2v symmetry, in agreement with the results of earlier computational studies of 1-H at a different theoretical level, [2] and with the experimentally observed conformations of 1 [16] and complex 5. [8] As the molecular structures of 3-H, 6-H, 5-H, and 7-H allow no clear-cut separation between orbitals of σ-and π-symmetry, we re-optimised the structures of these species under the constraint of C s symmetry.…”

Section: Computational Studiesmentioning

confidence: 99%

“…[2,3] Although electron delocalisation over the phosphonio groups and the π-electron system is low, [2,4] the electrostatic influence of the substituents still induces a marked reduction in nucleophilicity relative to the anionic phospholide derivatives, and polarises the π-electron distribution in the ring. [2Ϫ4] As a consequence of these effects, bis(phosphonio)benzophospholides display a very balanced nucleophilic and electrophilic reactivity, which is the primary reason for their remarkable stability towards solvolysis and addition reactions, [1,3,5] and their preference to coordinate to transition metal atoms through the phosphorus lone-pair [3,6] rather than the π-electron system as most other phospholide-type ligands.…”

Section: Introductionmentioning

confidence: 98%

“…This view is, in principle, supported by the results of a comparative theoretical study of the parent benzo[c]phospholide anion and the corresponding bis(phosphonio)-substituted cation. [2] However, a concise investigation with regard to this issue is still lacking. Scheme 1 In the present work we present a combined experimental and computational study of the molecular and electronic structures of the neutral 1-(triphenylphosphonio)enzo[c]-phospholides 2 and 3, the borane adduct 6, and the thioxophosphorane derivative 7 (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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Structural and Electronic Properties of Neutral Phosphoniobenzo[c]phospholides

Häp

Szarvas

Nieger

et al. 2001

Eur. J. Inorg. Chem.

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The neutral monophosphoniobenzo[c]phospholides 2 and 3 were selectively prepared by reduction of bis(triphenylphosphonio)benzophospholide chloride 1[Cl]. Compound 3 was further converted into the borane adduct 6 and the thioxophosphorane 7. All products were characterised by spectroscopic methods and X-ray diffraction. The most notable features of the molecular structures are the significantly different distances of the two P−C bonds adjacent to the two-coordinate phosphorus atom (P2−C1 175.0−176.6, P2−C3 171.7−173.5 pm), and a short exocyclic C−P(phosphonio) bond (C1−P1 172.5−173.7 pm) relative to cationic derivatives such as 1. Structure comparisons revealed further variations in the bond lengths, which can be related to the changes in

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Section: Syntheses and Spectroscopic Investigationsmentioning

confidence: 99%

Section: Crystal Structure Studiesmentioning

confidence: 99%

Section: Computational Studiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Structural and Electronic Properties of Neutral Phosphoniobenzo[c]phospholides

Häp

Szarvas

Nieger

et al. 2001

Eur. J. Inorg. Chem.

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Reduction of Bis(phosphonio)isophosphindolides to Phosphane-Functionalized Benzo[c]phospholides

Gudat¹,

Bajorat²,

Häp³

et al. 1999

Eur. J. Inorg. Chem.

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Keywords: Phosphorus heterocycles / Phospholides / Nickel complexes / Reductions / NMR spectroscopy Bis(phosphonio)benzo[c]phospholides (isophosphindolides) alkali metals followed a more complicated course and gave a mixture of 2, 3, and the substitution product 8, which was 1a,b have been found to react with magnesium or alkali metal naphthalenides MC 10 H 8 (M = Li, Na, K) with reduction further reduced to the phosphanido-substituted benzo-[c]phospholide 9. The latter could be formed selectively by of one or both of the phosphonio groups. The main products are the mono-or bis(phosphanyl)-substituted heterocycles 2, first converting 1a into 8 by treatment with PhNa and then treating this with lithium. NMR data of the phosphane-3, 6, 7, which have been characterized by in situ NMR studies and in some cases isolated. Subsequent reaction of 2 with substituted benzo[c]phospholides and the structural features of 4 are discussed. excess [Ni(CO) 4 ] gave the complex 4, which has been characterized by X-ray diffractometry. Reactions of 1a with proceed with selective cleavage of one PϪC bond in each

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η2(π)-Coordination of a Bis-Phosphonio-Benzophospholide Cation: A Novel Complexation Mode for Unsaturated Phosphorus Heterocycles

Gudat¹,

Häp²,

Nieger³

2001

Z. anorg. allg. Chem.

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The bis-phosphonio-benzo[c]phospholide tetraphenylborate 4[BPh 4 ] reacts with CpCo(C 2 H 4 ) 2 to form a chelate complex [Co(g 5 ±Cp)(j 2 P,g 2 (P=C)±4)][BPh 4 ] (6[BPh 4 ]) which was characterized by means of spectroscopic techniques and a single crystal X-ray diffraction study. The observed g 2 (p)-coordination of the benzophospholide moiety in the cation 6 is highly unusual for aromatic phosphorus heterocycles. The structural data suggest a pronounced coordination-induced localization of p-electrons in the condensed ring system.

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Cited by 13 publications

References 0 publications

Structural and Electronic Properties of Neutral Phosphoniobenzo[c]phospholides

Structural and Electronic Properties of Neutral Phosphoniobenzo[c]phospholides

Reduction of Bis(phosphonio)isophosphindolides to Phosphane-Functionalized Benzo[c]phospholides

η2(π)-Coordination of a Bis-Phosphonio-Benzophospholide Cation: A Novel Complexation Mode for Unsaturated Phosphorus Heterocycles

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