Synthese und Charakterisierung stabiler Bis(phosphonio)isophosphindolylium‐Carbonylmetallate und eines kationischen Bis(phosphonio)isophosphindolylium‐Gold‐Komplexes

Gudat, Dietrich; Nieger, Martin; Schrott, Martin

doi:10.1002/cber.19951280309

Cited by 32 publications

(28 citation statements)

References 18 publications

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“…The molecular structures are shown in Figure 1, and selected bond lengths are given in Table 3. The corresponding data of the cation 1 [16] and the anionic complex 5 [8] were included for comparison.…”

Section: Crystal Structure Studiesmentioning

confidence: 99%

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: Crystal Structure Studiesmentioning

confidence: 99%

Structural and Electronic Properties of Neutral Phosphoniobenzo[c]phospholides

Häp

Szarvas

Nieger

et al. 2001

Eur. J. Inorg. Chem.

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“…ocyclic PϪC distances (1.774Ϫ1.789 Å ) are longer than the Comparison of δ 31 P values for the corresponding nuclei corresponding bonds in 1a (1.747Ϫ1.749 Å [14] ) but shorter in the lithium and sodium salts of the anions 2, 3, and 9 than the peripheral PϪC(phenyl) distances (1.825Ϫ1.847 indicates some influence of the counterion, which is less Å ). The PϪNi distances in 4 are comparable with typical pronounced for the monoanions 2, 3 than for 9 and sug-values in PPh 3 ϪNi complexes (2.225 ± 0.070 Å ).…”

Section: P-mentioning

confidence: 93%

“…The bonding parameters in the fused ring systems of the from the two-coordinate phosphorus atom to the adjacent anions do not differ significantly from those in the phoscarbon atoms, which tends to impose some "ylidic" charac-phonio-substituted cation 1a. [14] On the other hand, the exter on the PϪC bond.…”

Section: P-mentioning

confidence: 98%

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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Bis(phosphonio)benzo[c]phospholides (isophosphindolides) 1a,b have been found to react with magnesium or alkali metal naphthalenides MC10H8 (M = Li, Na, K) with reduction of one or both of the phosphonio groups. The main products are the mono‐ or bis(phosphanyl)‐substituted heterocycles 2, 3, 6, 7, which have been characterized by in situ NMR studies and in some cases isolated. Subsequent reaction of 2 with excess [Ni(CO)4] gave the complex 4, which has been characterized by X‐ray diffractometry. Reactions of 1a with alkali metals followed a more complicated course and gave a mixture of 2, 3, and the substitution product 8, which was further reduced to the phosphanido‐substituted benzo[c]phospholide 9. The latter could be formed selectively by first converting 1a into 8 by treatment with PhNa and then treating this with lithium. NMR data of the phosphane‐substituted benzo[c]phospholides and the structural features of 4 are discussed.

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“…No contacts closer than van der Waals distances upfield 31 P resonance in a 1 H, 31 P-HMQC spectrum re-are exhibited by any of the single components. As in 1 [9] , vealed that the splitting must arise from coupling with the the fused ring system in the cation 8a ( Figure 1) is planar, two exocyclic phosphorus nuclei rather than the single en-with a standard deviation of the ring atoms and the two docyclic phosphorus nucleus. The magnitude of the n J HP exocyclic phosphorus atoms from the mean plane of 0.030 couplings [J ϭ ϩ(Ϫ)3.3 and Ϫ(ϩ)1.7 Hz] which were deter-Å .…”

Section: Nmr-spectroscopic Investigationsmentioning

confidence: 96%

“…The magnitude of the n J HP exocyclic phosphorus atoms from the mean plane of 0.030 couplings [J ϭ ϩ(Ϫ)3.3 and Ϫ(ϩ)1.7 Hz] which were deter-Å . The difference between endocyclic [1.695(4), 1.697(4) Å ] mined by iterative analysis suggested attachment of the hy-and exocyclic PϪC bond lengths [1.723(4), 1.729(4) Å ] is drogen atoms in the 4,7 rather than in the remote 5,6 posi-similar to 1 [9] , but both types of bonds are somewhat tions of the fused ring system. This hypothesis was further shorter than there.…”

Section: Nmr-spectroscopic Investigationsmentioning

confidence: 98%