Tetra-n-propyl-1,2-dithioxodi-λ5-phosphane

Sillanpää, Reijo; Ergin, Ömer; Celebi, S.

doi:10.1107/s0108270192007625

Cited by 4 publications

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“…With the characterization of the phosphorus chemical shift tensor in TMPS, this correlation can be examined more rigorously. Table lists the phosphorus chemical shift data and the C−P−C bond angle for [R 2 P(S)] 2 where R = methyl (this work), ethyl, n -propyl, or n -butyl …”

Section: Discussionmentioning

confidence: 99%

“… a This work. b Reference 6. c NMR data from ref , X-ray crystal structure from ref . d NMR data from ref , no crystal structure available. …”

Section: Discussionmentioning

confidence: 99%

“…15 With the characterization of the phosphorus chemical shift tensor in TMPS, this correlation can be examined more rigorously. Table 7 lists the phosphorus chemical shift data and the C-P-C bond angle for [R 2 P(S)] 2 where R ) methyl (this work), ethyl, 6 n-propyl, 44 or n-butyl. 17 It is difficult to draw any definite conclusion based on the first three compounds in the series, partly due to the experimental uncertainty in the C-P-C bond angle; however, it appears that the isotropic shielding trend does not follow the bond angle, i.e., increasing bond angle does not correlate directly with an increase in the isotropic chemical shift.…”

Section: Discussionmentioning

confidence: 99%

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Phosphorus Chemical Shift Tensors for Tetramethyldiphosphine Disulfide: A ³¹P Single-Crystal NMR, Dipolar-Chemical Shift NMR, and Ab Initio Molecular Orbital Study

et al. 2000

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Phosphorus chemical shift and spin-spin coupling tensors have been characterized for tetramethyldiphosphine disulfide (TMPS) by analysis of 31 P CP NMR spectra obtained at 4.7 T for a single crystal. In addition, 31 P CP NMR spectra of stationary powder and magic angle spinning (MAS) samples have been acquired at two applied magnetic fields (4.7 and 9.4 T) and analyzed independently using the dipolar-chemical shift method. A 2D spin-echo NMR spectrum was also obtained to independently determine the effective 31 P-31 P dipolar coupling constant. The crystal structure of TMPS (space group C2/m) consists of six molecules per unit cell. For two of the six molecules, the two phosphorus nuclei are related by an inversion center (site 1), while the remaining four molecules possess mirror planes containing the S-P-P-S bonds (site 2). The differences between the two sites are very subtle, as revealed by a redetermination of the X-ray crystal structure. The phosphorus chemical shift tensors obtained from both single-crystal and dipolar-chemical shift NMR methods are in excellent agreement. For site 1, δ 11 ) 91 ppm, δ 22 ) 75 ppm, and δ 33 ) -63 ppm with an error of (2 ppm for each component. The principal components of the phosphorus chemical shift tensor at site 2 are very similar; δ 11 ) 92 ppm, δ 22 ) 74 ppm, and δ 33 ) -59 ppm, again with errors of (2 ppm. The phosphorus chemical shift tensors for both sites are oriented such that the direction of highest shielding is closest to the P-S bond while the direction of least shielding is perpendicular to the plane containing the S-P-P-S bonds. Ab initio (RHF and DFT) calculations of the phosphorus chemical shift tensors for both sites are in good agreement with experiment.

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Section: Discussionmentioning

confidence: 99%

“… a This work. b Reference 6. c NMR data from ref , X-ray crystal structure from ref . d NMR data from ref , no crystal structure available. …”

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Phosphorus Chemical Shift Tensors for Tetramethyldiphosphine Disulfide: A ³¹P Single-Crystal NMR, Dipolar-Chemical Shift NMR, and Ab Initio Molecular Orbital Study

et al. 2000

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ChemInform Abstract: Tetra‐n‐propyl‐1,2‐dithioxodi‐λ5‐phosphane

1993

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Reactivity Studies of [(thf)₂Mg{μ-C(CH₃)₂C₂H₄C(CH₃)₂}]₂: Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane

2016

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I n T H F s o l u t i o n [ { ( t h f ) 2 M g { μ -C -(CH 3 ) 2 C 2 H 4 (CH 3 ) 2 C}} 2 ] (1) exchanges the alkanediide ligand with [{(thf) 2 Mg{μ-CH 2 ) 5 }} 2 ] in an equilibrium leading to the formation of [{(thf) 2 Mg} 2 {μ-C(CH 3 ) 2 C 2 H 4 C(CH 3 ) 2 }{μ-(CH 2 ) 5 }](2). Depending on the crystallization temperature, homoleptic 1 or heteroleptic 2 crystallizes from THF solutions, verifying a temperature-dependent Schlenk equilibrium. Irradiation of a solution of 1 in [D 8 ]THF with UV light yields magnesium hydride and alkene via a β-hydride elimination reaction. In a metathetical approach dichlorophenylphosphane reacts with 1 in THF to give the intermediate "PhP(Cl){C(CH 3 ) 2 C 2 H 4 (CH 3 ) 2 CMgCl" (3-MgCl), which forms three subsequent products. In order to ease handling and characterization of these compounds, hydrolysis and oxidation with sulfur has been performed. This product mixture was separated by column chromatography, yielding the chlorophosphane sulfide [Ph(S)P(Cl){C-(CH 3 ) 2 C 2 H 4 (CH 3 ) 2 CH)}] (3-S), the cyclic phosphane sulfide [Ph(S)P{C(CH 3 ) 2 C 2 H 4 (CH 3 ) 2 C)}] (4-S), and the cyclic 1,1diphosphane disulfide [{(Ph(S)P} 2 {μ-C(CH 3 ) 2 C 2 H 4 (CH 3 ) 2 C}] (6-S 2 ). Furthermore, traces of the acyclic 1,1-diphosphane disulfides [{PhP(S)(C(CH 3 ) 2 C 2 H 4 CH(CH 3 ) 2 )}{PhP(S)(C(CH 3 ) 2 C 2 H 4 C(CH 3 )(CH 2 )}] (8-S 2 ) and meso-[{Ph(S)P(C-(CH 3 ) 2 C 2 H 4 (CH 3 ) 2 CH)} 2 ] (7-S 2 ) have also been isolated. Compounds 6−8 represent the phosphorus-containing products of indirect Grignard reductions.

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Tetra-n-propyl-1,2-dithioxodi-λ5-phosphane

Abstract: Ci2H28P2S2, Mr = 298.42, monoclinic, P21/n, a = 6.491 (2), b = 10.152 (1), c = 13.358 (1)A, /3=100.74(1) °, V=864.8(4) A 3, Z =2, Din= 1.135 (4), Dx = 1.146 gcm -3, A(Mo Ka) =

Cited by 4 publications

References 4 publications

Phosphorus Chemical Shift Tensors for Tetramethyldiphosphine Disulfide: A ³¹P Single-Crystal NMR, Dipolar-Chemical Shift NMR, and Ab Initio Molecular Orbital Study

Phosphorus Chemical Shift Tensors for Tetramethyldiphosphine Disulfide: A ³¹P Single-Crystal NMR, Dipolar-Chemical Shift NMR, and Ab Initio Molecular Orbital Study

ChemInform Abstract: Tetra‐n‐propyl‐1,2‐dithioxodi‐λ5‐phosphane

Reactivity Studies of [(thf)₂Mg{μ-C(CH₃)₂C₂H₄C(CH₃)₂}]₂: Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane

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Tetra-n-propyl-1,2-dithioxodi-λ5-phosphane

Abstract: Ci2H28P2S2, Mr = 298.42, monoclinic, P21/n, a = 6.491 (2), b = 10.152 (1), c = 13.358 (1)A, /3=100.74(1) °, V=864.8(4) A 3, Z =2, Din= 1.135 (4), Dx = 1.146 gcm -3, A(Mo Ka) =

Cited by 4 publications

References 4 publications

Phosphorus Chemical Shift Tensors for Tetramethyldiphosphine Disulfide: A 31P Single-Crystal NMR, Dipolar-Chemical Shift NMR, and Ab Initio Molecular Orbital Study

Phosphorus Chemical Shift Tensors for Tetramethyldiphosphine Disulfide: A 31P Single-Crystal NMR, Dipolar-Chemical Shift NMR, and Ab Initio Molecular Orbital Study

ChemInform Abstract: Tetra‐n‐propyl‐1,2‐dithioxodi‐λ5‐phosphane

Reactivity Studies of [(thf)2Mg{μ-C(CH3)2C2H4C(CH3)2}]2: Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane

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Phosphorus Chemical Shift Tensors for Tetramethyldiphosphine Disulfide: A ³¹P Single-Crystal NMR, Dipolar-Chemical Shift NMR, and Ab Initio Molecular Orbital Study

Phosphorus Chemical Shift Tensors for Tetramethyldiphosphine Disulfide: A ³¹P Single-Crystal NMR, Dipolar-Chemical Shift NMR, and Ab Initio Molecular Orbital Study

Reactivity Studies of [(thf)₂Mg{μ-C(CH₃)₂C₂H₄C(CH₃)₂}]₂: Scrambling Reactions and Diverse Reactions with Dichlorophenylphosphane