Structural and Electronic Properties of Neutral Phosphoniobenzo[c]phospholides

Häp, Stefan; Szarvas, László; Nieger, Martin; Gudat, Dietrich

doi:10.1002/1099-0682(200111)2001:11<2763::aid-ejic2763>3.0.co;2-v

Cited by 13 publications

(12 citation statements)

References 13 publications

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“…Table 1. phosphonio-benzo[c]phospholides (172.5 Ϫ 173.7 pm [10]). The endocyclic bond angles are similar in all compounds; the observed differences can be rationalised as a direct geometrical consequence of the bond length variations.…”

Section: Methodsmentioning

confidence: 99%

A Zwitterionic Phosphonio-1, 2, 4-Diazaphospholide and Neutral 1, 2, 4-Diazaphosphole — A Comparative Study of Molecular Structures and Co-ordination Properties

Szarvas

Bajko

Fusz

et al. 2002

Z. anorg. allg. Chem.

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The bis-phosphonio-1,2,4-diazaphospholide salt (1[Cl]) reacts with complex boron hydrides under selective extrusion of one PPh 3 moiety to give borane adducts of a novel zwitterionic phosphonio-1,2,4-diazaphospholide. Both the Et 3 B adduct 2b and the free zwitterionic heterocycle 3, which was liberated by further reaction of 2b with NEt 3 , were characterized by spectroscopic data and 2b, as well, by a single crystal X-ray diffraction study. The comparison of the structural data with those of a neutral 1,2,4-diazaphosphole and a lithium-1,2,4-diazaphospholide which was formed by deprotonation of the parent 1,2,4-diazaphosphole 4a discloses trends in endocyclic bonding distances which can be rationalized in terms of a charge dependent shift in the π-electron distribution. First studies of the co-ordination properties reveal for Ein Zwitterionisches Phosphonio-1,2,4-Diazaphospholid und Neutrales 1,2,4-Diazaphosphol ؊ Eine Vergleichende Studie von Molekülstrukturen und KoordinationseigenschaftenInhaltsübersicht. Das Bis-phosphonio-1,2,4-diazaphospholid-Salz (1[Cl]) reagiert mit komplexen Borhydriden unter selektiver Abspaltung einer PPh 3 -Gruppe zu Boranaddukten eines neuen zwitterionischen Phosphonio-1,2,4-diazaphospholids. Sowohl das Et 3 B-Addukt 2b als auch der freie zwitterionische Heterocyclus 3, der durch weitere Reaktion von 2b mit NEt 3 freigesetzt wurde, wurden durch spektroskopische Daten und 2b zusätzlich durch eine Einkristall-Röntgenstrukturanalyse charakterisiert. Der Vergleich der Strukturdaten mit denen eines neutralen 1,2,4-Diazaphosphols und eines Lithium-1,2,4-diazaphospholids, das durch Deprotonierung der Stammverbindung 1,2,4-Diazaphosphol 4a erhalten wurde, zeigen Trends in den endocyclischen Bindungslängen, die im Sinne ladungsabhängiger Variationen der π-Elektronenvertei-

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Section: Methodsmentioning

confidence: 99%

A Zwitterionic Phosphonio-1, 2, 4-Diazaphospholide and Neutral 1, 2, 4-Diazaphosphole — A Comparative Study of Molecular Structures and Co-ordination Properties

Szarvas

Bajko

Fusz

et al. 2002

Z. anorg. allg. Chem.

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“…The benzo[c]phospholide derivatives (Entries 13 and 14) are a special case [79]. Coupling the experimental data with theoretical calculations indicate that the ring C-P bond has considerable double bond character, and the interaction with the benzene ring is such that the entire ion can be considered a 10 -electron system.…”

Section: Physical Properties Of Phospholesmentioning

confidence: 98%

“…Much of this work is concerned with coordination chemistry of the species, but pertinent to the present discussion is a recent study which described modification of the phosphonio group or groups to give simpler species. Thus, reduction of 186 by sodium borohydride caused cleavage of one phosphonio group to give the overall neutral but dipolar species 187, a stable yellow crystalline solid [78,79] (Equation 59). Also, it was possible to convert one or both phosphonio groups of 186 to the phosphino group, again giving stable substances, 188 [79] and 191 [80].…”

Section: Benzophospholesmentioning

confidence: 99%

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The Continuing Development of the Chemistry of Phospholes

Quin¹

2006

COC

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The last five years have seen many advances in the chemistry of phospholes. Motivating much of the work has been the potential for discovering valuable applications of phospholes, especially as ligands in metal coordination compounds designed for use as homogeneous catalysts, and in the field of electro-optical substances. This review covers the research in the synthesis, properties and applications of phospholes that has been published since the last comprehensive review by the author in 1999. While prepared for the specialist, the review is designed to introduce some of the aspects of phosphole chemistry to the general reader.

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“…The ring system of the η 1 (P)‐coordinated phosphoniobenzophospholide in 5 b (Figure 1) is essentially planar. The exocyclic P2C2 bond (174.7(3) pm) is longer and the endocyclic P1C2 (175.0(3) pm) and P1C9 bonds (169.9(3) pm) are shorter than in free 1 (P2C2 172.55(11), P1C2 176.62(11), P1C9 171.71(14) pm16) and resemble the corresponding bonds in the chromium complex 2 (P2C2 174.4(1), P1C2 176.7(2), P1C9 169.1(2) pm7a). The remaining intraligand bond lengths are identical in all three compounds within experimental accuracy.…”

Section: Resultsmentioning

confidence: 97%

Redox‐Induced Coordination Isomerization of a Phosphoniobenzophospholide

Gudat

Lewall

Nieger

et al. 2003

Chemistry A European J

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1-Triphenylphosphoniobenzo[c]phospholide 1 reacts with [M(CO)(5)Br] (M = Mn, Re) and [Mn(CO)(3)(naphthalene)][BF(4)] to give complexes cis-[M(CO)(4)(1)Br] (5 a,b) and [Mn(CO)(3)(1)][BF(4)] (6 a[BF(4)]), respectively, featuring eta(1)(P)- and eta(5)(pi)-coordination of the phosphole ring. The corresponding reactions with [M(2)(CO)(10)] proceed with conservation of the metal-metal bond and yield, depending on the reaction temperature, dinuclear complexes [M(2)(CO)(8)(1)] (M=Mn, 7 a) or [M(2)(CO)(6)(1)(2)] (M=Mn, Re, 8 a,b) with mu(2)-bridging eta(1)(P):eta(2)(Pdbond;C) coordination of the phosphole moiety. All complexes formed were characterized by spectroscopic data; 5 b, 6 a[BF(4)], and 8 a,b were characterized by X-ray diffraction studies as well. The structural and (31)P NMR data of the dinuclear manganese complex 8 a suggest that the interaction between the metal atoms and the eta(2)-bound Pdbond;C double bond moieties is dominated by the L-->M charge-transfer contribution; this hints at a very low back-donation ability of the central M(2)(CO)(6) fragment. Investigation of the reactions of the Mn complexes 6 a and 8 a with Mg or ferrocenium hexafluorophosphate ([Fc][PF(6)]), respectively, revealed that the chemically reversible mutual interconversion between both species was feasible. Likewise, oxidation of the rhenium complex 8 b with [Fc][PF(6)] gave spectroscopic evidence for the formation of a Re analogue of 6 a. Electrochemical studies suggested that the oxidation 8 a-->2 6 a involves two consecutive single-electron-transfer steps, the first of which is electrochemically reversible and produces a metastable radical cation that is detectable by ESR spectroscopy. The mutual interconversion between 6 a and 8 a represents the first case of a reversible coordination isomerization of a phosphaarene that is triggered by a redox process and might stimulate further studies directed at the use of dinuclear phosphaarene complexes in redox-catalysis.

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Structural and Electronic Properties of Neutral Phosphoniobenzo[c]phospholides

Cited by 13 publications

References 13 publications

A Zwitterionic Phosphonio-1, 2, 4-Diazaphospholide and Neutral 1, 2, 4-Diazaphosphole — A Comparative Study of Molecular Structures and Co-ordination Properties

A Zwitterionic Phosphonio-1, 2, 4-Diazaphospholide and Neutral 1, 2, 4-Diazaphosphole — A Comparative Study of Molecular Structures and Co-ordination Properties

The Continuing Development of the Chemistry of Phospholes

Redox‐Induced Coordination Isomerization of a Phosphoniobenzophospholide

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