Phosphorus-31 and selenium-77 nuclear magnetic resonance spectra of phosphorus-poor phosphorous selenide compounds

Baldus, H. P.; Blachnik, R.; Loennecke, P.; Tattershall, Bruce W.

doi:10.1039/dt9910002643

Cited by 15 publications

(4 citation statements)

References 13 publications

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“…the distances Se a ؒ ؒ ؒ Se b and Se a ؒ ؒ ؒ Se B would be different. There would therefore be a low-energy path for deformation through the boat form with C 2v symmetry to the enantiomer twisted in the opposite sense, and it would not be surprising that all selenium atoms in the six-membered ring appear chemically equivalent on the NMR time-scale, 22 even at 240 K. 23 To investigate this, we constrained the ab initio optimisations of geometry for P 2 Se 5 only to C 2 rather than to C 2v symmetry in calculations using the STO-3G, 3-21G* or ECP bases, but Table 2 shows that the twist angle P A ᎐Se B ᎐Se b ᎐P C is predicted to be zero, probably to within the accuracy of these methods. The C 2v symmetry is thus confirmed.…”

Section: Ab Initio Molecular Structure Predictionmentioning

confidence: 99%

Crystal structure determination and ab initio molecular structure prediction for exo,exo-α-P4Se3(CN)2 , the first phosphorus selenide cyanide

Tattershall¹,

Sandham²,

Clegg³

1997

J. Chem. Soc., Dalton Trans.

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Bicyclic exo,exo-α-P 4 Se 3 (CN) 2 1 was made by reaction of α-P 4 Se 3 I 2 with AgCN, and its crystal structure determined from X-ray data collected at 160 K. Molecular structures were predicted for exo,exo-α-P 4 Se 3 (CN) 2 , exo,exo-α-P 4 S 3 (CN) 2 and P 2 Se 5 2 by restricted Hartree-Fock ab initio molecular-orbital calculations using STO-3G, 3-21G* and LanL2DZ(d) ECP basis sets, and for P 2 Se 5 additionally using Ahlrichs' split-valence and triplezeta valence basis sets. Comparisons with the crystal structure of exo,exo-α-P 4 Se 3 (CN) 2 and with a previously published crystal structure of P 2 Se 5 showed that the 3-21G* basis sets gave sufficiently good predictions for most bond angles that the effects on them of intermolecular interactions in the crystals could be discussed.

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Section: Ab Initio Molecular Structure Predictionmentioning

confidence: 99%

Crystal structure determination and ab initio molecular structure prediction for exo,exo-α-P4Se3(CN)2 , the first phosphorus selenide cyanide

Tattershall¹,

Sandham²,

Clegg³

1997

J. Chem. Soc., Dalton Trans.

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“…The appearance of isomer ii in a concentration exceeding that of isomer 3 may have resulted from a racemisation reaction of isomer i, which is a kinetic product of the sulfurisation reaction. A skeletal rearrangement reaction with k, 800 SKI at 297 K is known for P,Se,I 6 (X = I), in which Se, becomes bonded to P, as iodine becomes bonded to PA, probably by an intramolecular mechanism [9]. The result is conversion of one enantiomer to the other.…”

Section: Sulfurisation Reactionsmentioning

confidence: 99%

“…Study of variations in 31P NMR chemical shifts and coupling constants with structure has helped elucidate Bicyclic phosphorus chalcogenide compounds which the geometric and electronic factors which control these carry exocyclic groups have proved a fruitful area of syn-parameters in polycyclic molecules [5, 121. These thetic chemistry, giving compounds in the series 01-or pmolecular skeletons all contain only three-coordinate P,E3XY (E = S, Se) [I -81 or recently P,E,X [9] or phosphorus, and in order to discover new series of P,S,X [lo, 111, where the exocyclic X or Y are halide, molecules, we wished to make cyclic phosphorus pseudohalide, or various N-, 0-, Po r S-centred groups.…”

Section: Introductionmentioning

confidence: 99%

Sulfurisation of Amino Tetraphosphorus Trichalcogenide Compounds

Tattershall¹,

Sandham²

1996

Zeitschrift anorg allge chemie

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Amino tetraphosphorus trisulfides α‐P4S3(NR1R2)2 reacted with S8 under photolysis using visible light, in moderate or low conversion, to give α‐P4S3(S)(NR1R2)2, in which the added sulfur atom was exocyclic. For NR1R2 = NPr2i, three isomers were found: a pair of diastereomers corresponding to attachment of the sulfur atom to a nitrogen‐carrying phosphorus atom either with retention or with inversion of its configuration, and an isomer containing a sulfurised bridgehead phosphorus atom. For NR1R2 = NMePh, only the two diastereomers were seen. Photolysis of a mixture of α‐P4Se3(NMePh)2 and α‐P4Se3(NMePh)I with S8 gave as major products α‐P4SSe2(NMePh)2 and α‐P4SSe2(NMePh)I, in which sulfur had replaced the bridging selenium atom in the starting compounds. This provides a synthesis of compounds α‐P4SSe2XY in which sulfur occupies a specific skeletal position, rather than being randomly distributed. All products were characterised by 31P NMR in unseparated solutions. Ab initio MO calculations of geometry and of GIAO NMR chemical shifts at the 3‐21G* level for three isomers of the unknown model compound α‐P4S3(S)(NH2)2, and two isomers of α‐P4S3(NH2)2, allowed identification of the observed isomer of α‐P4S3(S)(NPr2i)2 with a sulfurised bridgehead, but relative assignment of the two diastereomers to their NMR parameters remains a hypothesis.

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“…While the related cage compound P 3 Se 4 I undergoes a rapid skeletal rearrangement reaction in solution in CS 2 , involving simultaneous exchange of the exocyclic iodide substituent between phosphorus atoms, no dynamic NMR effects were observed for the corresponding thiolate P 3 Se 4 (SEt), even at 370 K [10].…”

Section: Introductionmentioning

confidence: 99%

Insertion of Methylthiirane into the P–I Bonds of α‐P₄S₃I₂

Tattershall

Geneux

Holmes

et al. 2009

Zeitschrift anorg allge chemie

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Phosphorus-31 and selenium-77 nuclear magnetic resonance spectra of phosphorus-poor phosphorous selenide compounds

Cited by 15 publications

References 13 publications

Crystal structure determination and ab initio molecular structure prediction for exo,exo-α-P4Se3(CN)2 , the first phosphorus selenide cyanide

Crystal structure determination and ab initio molecular structure prediction for exo,exo-α-P4Se3(CN)2 , the first phosphorus selenide cyanide

Sulfurisation of Amino Tetraphosphorus Trichalcogenide Compounds

Insertion of Methylthiirane into the P–I Bonds of α‐P₄S₃I₂

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Phosphorus-31 and selenium-77 nuclear magnetic resonance spectra of phosphorus-poor phosphorous selenide compounds

Cited by 15 publications

References 13 publications

Crystal structure determination and ab initio molecular structure prediction for exo,exo-α-P4Se3(CN)2 , the first phosphorus selenide cyanide

Crystal structure determination and ab initio molecular structure prediction for exo,exo-α-P4Se3(CN)2 , the first phosphorus selenide cyanide

Sulfurisation of Amino Tetraphosphorus Trichalcogenide Compounds

Insertion of Methylthiirane into the P–I Bonds of α‐P4S3I2

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Insertion of Methylthiirane into the P–I Bonds of α‐P₄S₃I₂