Analysis of substituent effects on31P NMR chemical shifts: PX2Y molecules

Dransfeld, Alk; Schleyer, Paul von Ragué

doi:10.1002/(sici)1097-458x(199806)36:13<s29::aid-omr288>3.0.co;2-t

Cited by 16 publications

(10 citation statements)

References 2 publications

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“…Associated is a stepwise increase of the 29 Si chemical shift, as can be gathered from Table 2. This substitution effect on δ ( 29 Si) is not linear, but instead shows a sagging behavior, as previously reported for silanes 56, 58…”

Section: Resultssupporting

confidence: 78%

“…The electronegativity of the substituents is often correlated with the chemical shift with differing significance 58. We find that the linear relationships between the substituent electronegativity sum, Σ(EN), and δ ( 29 Si) (correlation coefficient square, cc =0.71) as well as between the inversion barrier and δ ( 29 Si) ( cc =0.72) are not high enough to provide a precise predictive tool.…”

Section: Resultsmentioning

confidence: 84%

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Silylanions: Inversion Barriers and NMR Chemical Shifts

Flock

Marschner

2002

Chem. Eur. J.

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Section: Resultssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 84%

Silylanions: Inversion Barriers and NMR Chemical Shifts

Flock

Marschner

2002

Chem. Eur. J.

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“…Even the structurally very similar Z and E isomers of 7‐phosphanorbornenes 1 differ by as much as 70 ppm in 31 P NMR chemical shifts 3. The advance of computing capacity allows for theoretical analyses of experimental systems 2a. 4, 5 Chesnut et al 4.…”

Section: Introductionmentioning

confidence: 99%

Fused Tricyclic Phosphiranes—Analysis of Phosphorus Chemical Shieldings

Couzijn

Ehlers

Slootweg

et al. 2008

Chemistry A European J

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1,2‐Addition of transient W(CO)5‐complexed phosphinidenes exo to hexamethyl Dewar benzene affords the novel 3‐phosphatricyclo[3.2.0.02,4]hept‐6‐ene complexes. The fused tricyclic phosphiranes are obtained as both the Z and the thermally less stable E isomers, the 31P NMR chemical shifts of which differ by about 60 ppm. A computational investigation shows that the phosphorus pyramidalization and the presence of the γ double bond are responsible for this effect. The semiquantitative results contribute to a more systematic understanding of the structural influences on 31P chemical shieldings. The congested double bond of the Z isomer can be epoxidized with m‐chloroperbenzoic acid (MCPBA) to afford a fused tetracyclic P,O bis‐adduct.

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“…The alkali-metal dihydrogenphosphanides are easily accessible PH 2 transfer reagents and valuable synthons for a wide variety of organophosphorus compounds . The NMR spectroscopic characterization of MPH 2 species with M = Li, Na, K, Rb, Cs as well as their structural characterization has given detailed insight into the physical properties of these compounds. Due to the instability of LiPH 2 at room temperature 3 base adducts of this compound have been prepared which are soluble in ethers and can be handled at room temperature …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structures of Lithium and Potassium Complexes of Phosphanyl-Substituted Bis[1,3-bis(trimethylsilyl)cyclopentadienyl]yttriates

et al. 2002

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The metathesis reaction of [(THF)4Li][Cp‘ ‘2Li] (1) (Cp‘ ‘ = 1,3-(Me3Si)2C5H3) with yttrium trichloride yields bis(tetrahydrofuran)lithium bis[1,3-bis(trimethylsilyl)cyclopentadienyl]dichloroyttriate (2). The metathesis reaction of 2 with potassium (triisopropylsilyl)phosphanide in toluene gives a stepwise exchange of the chloride ligands with the phosphanide substituents. In contrast to bis(tetrahydrofuran)lithium bis[1,3-bis(trimethylsilyl)cyclopentadienyl][(triisopropylsilyl)phosphanyl]chloroyttriate (3), which appears as an intermediate observable by NMR spectroscopy, (tetrahydrofuran)lithium bis[1,3-bis(trimethylsilyl)cyclopentadienyl][bis(triisopropylsilyl)phosphanyl]yttriate (4) is isolated as a colorless crystalline material with a YP2Li cycle and Y−P bond lengths of 2.840 Å. In solution a dissociation is observed into lithium (triisopropylsilyl)phosphanide and the THF complex of bis[1,3-bis(trimethylsilyl)cyclopentadienyl][(triisopropylsilyl)phosphanyl]yttrium (5). The reaction of either 2 or 4 with potassium (triisopropylsilyl)phosphanide in benzene yields (η6-benzene)potassium bis[1,3-bis(trimethylsilyl)cyclopentadienyl][bis(triisopropylsilyl)phosphanyl]yttriate (6) with a YP2K cycle and Y−P distances of 2.846 Å. The metathesis reaction of 2 with (DME)LiPH2 gives (1,2-dimethoxyethane)lithium bis[1,3-bis(trimethylsilyl)cyclopentadienyl]bis(phosphanyl)yttriate, which reacts with TMEDA to give colorless bis[(TMEDA)lithium] bis[1,3-bis(trimethylsilyl)cyclopentadienyl]bis(phosphanyl)yttriate chloride (7). The central YP2Li2Cl cycle is nearly planar with Y−P bond lengths of 2.849 Å.

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Analysis of substituent effects on31P NMR chemical shifts: PX2Y molecules

Cited by 16 publications

References 2 publications

Silylanions: Inversion Barriers and NMR Chemical Shifts

Silylanions: Inversion Barriers and NMR Chemical Shifts

Fused Tricyclic Phosphiranes—Analysis of Phosphorus Chemical Shieldings

Synthesis and Structures of Lithium and Potassium Complexes of Phosphanyl-Substituted Bis[1,3-bis(trimethylsilyl)cyclopentadienyl]yttriates

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