Die stabilisierung von tris(amino)phosphin durch komplexbildung

Nöth, Heinrich; Reith, H.; Thorn, Volker

doi:10.1016/s0022-328x(00)82315-3

Cited by 13 publications

(6 citation statements)

References 8 publications

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“…It should be possible to prepare complexes of [1,3,2]dioxaphosphepin ligands with a variety of functional groups using the nucleophilic displacement reactions of transition-metal-coordinated 2-chloro-[1,3,2]dioxaphosphepin ligands. Such reactions with chlorophosphines − and chlorophosphites derived from aliphatic diols − are a versatile method for the formation of complexes with unusual phosphorus-donor ligands. The coordination of the ligand to the transition metal stabilizes the phosphorus(III) oxidation state while maintaining a reactive phosphorus center.…”

Section: Introductionmentioning

confidence: 99%

Nucleophilic Displacement Reactions of cis-Bis((2,2‘-biphenylylene)phosphochloridite ester)tetracarbonylmolybdenum(0). The First Example of an Unusual Hydrolysis Reaction Yielding Unsymmetrically Substituted Products

et al. 2003

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Ligands containing groups derived from bis(aryl)diols are widely used in asymmetric catalysis; however, few studies of the conformations of these ligands in transition-metal complexes have been reported. In this paper, the nucleophilic displacement reactions of cis-Mo(CO)4(2,2‘-C12H8O2PCl)2 (1) have been used to prepare a variety of complexes with [1,3,2]dioxaphosphepin ligands, and the conformations of these ligands have been studied by NMR spectroscopy and X-ray crystallography. The nucleophilic substitution reactions yield both the expected disubstituted complexes cis-Mo(CO)4(2,2‘-C12H8O2PXR)2 (XR = NPrn (2), OMe (4), SC6H4-4-Me (6)) and the unexpected hydrolysis products [R‘3NH][cis-Mo(CO)4(2,2‘-C12H8O2PO)(2,2‘-C12H8O2PXR)] (R‘3 = PrnH2, XR = NPrn, 3; R‘3 = Et3; XR = OMe, 5). NMR studies have demonstrated that the hydrolysis product is the major product when more than a minute amount of water is present, even in the presence of a large excess of the nucleophiles. This reaction is complete in approximately 90 min at 25 °C. A very surprising feature of this reaction is that substitution of one chloride in 1 by the RX- nucleophile greatly enhances the rate of substitution of the second chloride either by water or by another RX- nucleophile. NMR studies of the [1,3,2]dioxaphosphepin complexes in chloroform-d solution suggest that the R* and S* enantiomers of the ligands interconvert via a low-energy pathway. Crystal structures of the complexes demonstrate that both the R*S* diastereomer (1) and racemic mixtures of the R*R* and S*S* diastereomers (2−4) are observed in the solid state. These results suggest that bulkier biaryl groups are needed to prevent the racemization of the [1,3,2]dioxaphosphepin ligands in solution.

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Section: Introductionmentioning

confidence: 99%

Nucleophilic Displacement Reactions of cis-Bis((2,2‘-biphenylylene)phosphochloridite ester)tetracarbonylmolybdenum(0). The First Example of an Unusual Hydrolysis Reaction Yielding Unsymmetrically Substituted Products

et al. 2003

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“…Daß das Triaminophosphan P(NH2)3 mögliches Zwischenprodukt der PCI3-Ammonolyse sein kann, folgt aus der Reaktion zwischen Ammoniak und (C0)5MPC13 (M = Cr, Mo, W) [7]: es resultiert komplexstabilisiertes P(NH2)3. Ob P(NH2)3 aber tatsächlich bei der Ammonolyse von PCI3 als Zwischenprodukt auftritt, ist damit weiterhin offen, denn es ist nicht sicher, ob die Reaktion von PCI3 mit NH3 über die Stufen C12PNH2, C1P(NH2)2 zu P(NH2)3 schneller stattfindet als Kondensationsprozesse, die, ausgehend von C12PNH2 und C1P(NH2)2, zu mehrkernigen Produkten führen werden.…”

Section: Pp'p"-triaminocyclotriphosphazan Tetraphosphorhexaimid Tunclassified

“…Genannt seien (CO)5MP(NH2)3 [7], H3BP(NH2)3 [13] sowie (CO)5MP(NHNH2)3 [14] und (CO)5MP(NHNHCeH5)3 [15]. Es ist daher zu erwarten, daß auch Zwischen-und Folgeprodukte der PCl3-Ammonolyse durch Komplexbildung zu stabilisieren sind und damit nachweisbar sowie stukturell charakterisierbar werden.…”

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Ligandenstabilisierung durch Komplexbildung: P.P′.P″ -Triaminocyclotriphosphazan und adamantananaloges Tetraphosphorhexaimid / Stabilisation of Ligands by Complex Formation: P,P′,P″ -Triaminocyclotriphosphazane and an Adamantane-Analogous Tetraphosphorus Hexaimide

Nöth¹,

Thorn²

1981

Zeitschrift Für Naturforschung B

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Abstract The thermal decomposition of (CO)5MP(NH2)3 (M = Cr, Mo, W) has been studied. No definite products were obtained for M = W but the molybdenum complex yielded [(CO)5MoP]4(NH)6. The same type of complex results with M = Cr, in addition to [(CO)5CrP(NH)NH2]3. The pentacarbonylchromium groups may be removed from the adamantane type [(CO)5CrP]4(NH)6 with sulfur. The new compound S4P4(NH)6 results in this reaction. This compound is also a by-product in the thermal decomposition of SP(NH2)3. Attempts to prepare P4(NH)6 by desulfurisation from S4P4(NH)6 or from the chromium complex failed.

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“…The hydrolysis side product was unusual because it had not been observed in similar studies with the chlorodiphenylphosphines. [2][3][4][5][6][7][8][9][10][11] Hydrogen bonding was observed to play an important role in the crystal structures of the hydrolysis products. Because hydrogen bonding is becoming increasingly important in the assembly of nanostructures, [12][13][14][15] gels, 16 and polymers, 17 further investigation of hydrogen bonding in cis-tetracarbonylbis ([1,3,2]dioxaphosphepin)molybdenum(0) complexes is of interest.…”

Section: Introductionmentioning

confidence: 99%

Unusual Hydrolysis Reactions of cis-Bis((2,2‘-biphenylylene)phosphochloridite ester)tetracarbonylmolybdenum(0)

et al. 2004

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The hydrolysis of cis-Mo(CO) 4 (2,2′-C 12 H 8 O 2 PCl) 2 (1) in the presence of excess triethylamine and water yields [ 3) and free triethylamine in solution. The hydrolysis of 1 with a stoichiometric amount of triethylamine and water yields only 3. A Scatchard plot for the reaction of 3 and triethylamine to form 2 at 25 °C gives an equilibrium constant of 5.8 × 10 -3 for the reaction. Fitting the variabletemperature 31 P{ 1 H} NMR spectra of a CD 2 Cl 2 solution of 3 and 0.5 equiv of triethylamine using the gNMR program gives an activation energy of 47.4 kJ/mol for the reaction. The diastereomers of 3 crystallize with very different morphologies, allowing the X-ray crystal structures of both enantiomers to be determined. The 3R*R* diastereomer crystallizes in the noncentrosymmetric P2 1 2 1 2 1 space group, but the 3R*S* diastereomer crystallizes in the centrosymmetric P2 1 /c space group. The most interesting feature of the structures of 3R*R* and 3R*S* is the strong, intramolecular hydrogen bonding between the 2,2′-C 12 H 8 O 2 -POH and 2,2′-C 12 H 8 O 2 POligands that result in short O-O distances in both enantiomers (2.520(6) Å in 3R*R* and 2.373(11) Å in 3R*S*). The hydrogen bonding in both diastereomers is asymmetric, in contrast to previous speculation in the literature.

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Die stabilisierung von tris(amino)phosphin durch komplexbildung

Cited by 13 publications

References 8 publications

Nucleophilic Displacement Reactions of cis-Bis((2,2‘-biphenylylene)phosphochloridite ester)tetracarbonylmolybdenum(0). The First Example of an Unusual Hydrolysis Reaction Yielding Unsymmetrically Substituted Products

Nucleophilic Displacement Reactions of cis-Bis((2,2‘-biphenylylene)phosphochloridite ester)tetracarbonylmolybdenum(0). The First Example of an Unusual Hydrolysis Reaction Yielding Unsymmetrically Substituted Products

Ligandenstabilisierung durch Komplexbildung: P.P′.P″ -Triaminocyclotriphosphazan und adamantananaloges Tetraphosphorhexaimid / Stabilisation of Ligands by Complex Formation: P,P′,P″ -Triaminocyclotriphosphazane and an Adamantane-Analogous Tetraphosphorus Hexaimide

Unusual Hydrolysis Reactions of cis-Bis((2,2‘-biphenylylene)phosphochloridite ester)tetracarbonylmolybdenum(0)

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