Phosphorus–fluorine chemistry. Part XXII. Alkylthio- and arylthio-substituted fluorophosphoranes

Peake, S. C.; Schmutzler, Reinhard

doi:10.1039/j19700001049

Cited by 29 publications

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“…As 7, is thought to be known to better than 10 K in each case, it would appear that the barriers to rotation are indeed higher in compounds (3) and (4) than in compounds ( 5) and ( 6), and, since the two pairs of compounds differ only in that the latter are substituted at the 3-position on the piperidyl ring while the former are substituted at the 2-position, this seems to substantiate the importance of some form of steric interaction, either attractive in the form of an interaction between H and F in the ground state, or repulsive through steric crowding in the equatorial plane in the excited state. The difference in AG,Z between compounds (3) and (4) themselves would appear to favour the latter of these suggestions, since in (3) the bulky phenyl group in the equatorial plane would probably cause a greater degree of steric hindrance to rotation than would be expected from the methyl substituent in (4).…”

Section: Discussionmentioning

confidence: 99%

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Preparation and nuclear magnetic resonance study of phosphorus–fluorine compounds undergoing intramolecular exchange. Part 4. Rotameric forms of 1-piperidyltrifluorophosphoranes

Connelly¹,

Harris²

1984

J. Chem. Soc., Dalton Trans.

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Fluorine-1 9 and phosphorus-31 n.m.r. spectra are reported at variable temperature under conditions of proton decoupling for four 1 -piperidyltrifluorophosphoranes, substituted with a methyl group in the piperidyl ring so as to impart chirality. The axial fluorines are non-equivalent even at ambient probe temperature. As the temperature is lowered the spectrum shows evidence of two isomeric forms in each case, caused by the slowing of internal rotation about the P-N bond. The n.m.r. spectra were analysed to yield chemical shifts and coupling constants. The results are discussed in relation to conformation.Internal rotation about the P-N bond of aminofluorophosphoranes has been shown 1-3 to occur on a time-scale comparable to that associated with 19F n.m.r. A variety of effects on variable-temperature n.m.r. spectra may be observed depending on the symmetry and substitution pattern of the compounds concerned. In the case of aminofluorophosphoranes of the type (1) (excluding X = Y = F), if it is assumed that (i) pseudo-rotation at phosphorus is slow, (ii) the nitrogen envionment is effectively planar, and (iii) the potential minimum occurs when R' and R2 are in the plane formed by F', F2, P, and N (the axial plane), then there are two possible situations: (a) when R' = R2, then F' and FZ are equivalent for n.m.r. purposes under both fast-exchange and slow-exchange conditions of P-N internal rotation; (b) when R1 # R2, then F' and F2 become non-equivalent under conditions of slow P-N internal rotation.However, these conclusions ignore the nature of R1 and R2 and are only valid if these groups have effectively cylindrical symmetry (e.g. for CH, or CF,) or adopt suitable conformations (e.g. for CH3CHl when the methyl carbon is in the axial plane or is able to reorient rapidly about the C-N bond). If these conditions are not satisfied, then further complications may arise. For instance, Sanchez and Cowley have shown that if R' or R2 is chiral, then for the case X # Y diastereoisomerism occurs because there is a chiral axis along the P-N bond, so that under slow-exchange conditions four different axial fluorine environments may be detected by n.m.r. Even in the fast-exchange situation there are two different axial environments regardless of the relative populations of the two rotamers. It is assumed that neither X nor Y 1548 3. CHEM. SOC. DALTON TRANS. 1984 Table 1. Phosphorus-3 1 and fluorine-19 chemical shift data from ambient-temperature (308 K) spectra E(31P)/HZ = 40 478 568.8 e 40 479 180.0 40 478 466.2 e 40 479 107.8 e G(P)/p.p.m. -53.54 -53.5 -38.44 -56.07 -55 f -40.23 -55.6 G(Fa)/p*p.m. -42.57 -42.6 -30.39 -43.27 -43.4 -31.03 -43.5 G(F',)/p.p.m. -44.24 -44.3 -32.63 -43.50 -43.7 -31.19 -43.5 G(Fd/p.p.m. -67.86 -67.8 -68.23 -67.91 -69.1 -67.88-68.1 Absolute 31P frequency values (see the text). Phosphorus-31 chemical shifts are quoted with respect to the resonance of 85% H3P04, using the high-frequency-positive convention, and are obtained via the value of E(31P). Fluorine-19 chemical shifts are quoted with respect...

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Section: Discussionmentioning

confidence: 99%

“…15-20 K, whereas the opposite assignment (for, e.g., the a isomer) gives values for AG,* differing by up to ca. 4.2 kJ mol-' (ca. 1 kcal mol-l) using similar AT, values.…”

Section: Discussionmentioning

confidence: 99%

Preparation and nuclear magnetic resonance study of phosphorus–fluorine compounds undergoing intramolecular exchange. Part 4. Rotameric forms of 1-piperidyltrifluorophosphoranes

Connelly¹,

Harris²

1984

J. Chem. Soc., Dalton Trans.

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“…The mixture was stirred for 2 h (monitored by 31 P NMR) then evaporated to dryness. The resulting phosphorus species Ph 2 PÀCCÀPPh 2, [19] Ph 2 PÀNHPh, [20] Ph 2 POMe [21] or Ph 2 PSH [22] were extracted with pentane and characterized by comparison of their NMR data with that reported in the literature.…”

Section: Methodsmentioning

confidence: 99%

X−H (X=C, N, O, P, S) Bond Activations Induced byβ-Heterosubstituted Zirconaindenes

et al. 2001

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The azazirconacyclopentene-substituted phosphines 3 and 4 have been found to activate the C-H bonds of acetylenic systems, such as methylpropiolate, diphenylphosphinoacetylene and phenylacetylene, or of methylene compounds, such as malonitrile and diethylmalonate, to give complexes 5a-c, 6a and 6b. C-H bond activation also takes place with vinylacetate. Similar reactions with amines, alcohols, enolisable ketones, phenols, phosphonates, thiols and a second-generation SH-terminated dendrimer lead through X-H bond activation (X = N, O, P, S) to new complexes 8a-c, 9, 12 a,b, 13, 14a-c, 15, 16a and 16b. The azazirconacyclopentene-substituted amine 20 reacts to form analogous complexes. Zr-X bonds of these complexes (X = C, N, O, S) can be cleaved with diphenylchlorophosphine to give P-X phosphorus derivatives in high yield.

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“…B. E. Job et al proposed the treatment of sodium thiophenolate with a solution of diphenylchlorophosphine in diethyl ether under dry nitrogen in order to prepare the PPh 2 (SPh) ligand [46]. During the last 40 years, different synthetic routes of phenylthio(diphenyl)phosphine were the topic of further numerous articles [47][48][49][50][51][52].…”

Section: Preparation Of Eph 2 (Sph)mentioning

confidence: 99%

Synthesis and coordination chemistry of thiophenol-based heterodonor ligands containing P,S, As,S and P,SAs donor atoms

Sárosi

Silaghi‐Dumitrescu

Hey‐Hawkins

2013

Maced. J. Chem. Chem. Eng.

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This review article describes the synthesis and coordination chemistry of three types of thiophenol-based heterodonor ligands containing tertiary phosphine and/or arsine groups in combination with sulfur. Phenylthio(diphenyl)phosphine and -arsine ligands, EPh2(SPh) (E = P, As), incorporate an E–S bond in their structures. Upon reaction with different metal carbonyls, metal-mediated cleavage of the E–S bonds of these ligands has been observed, leading to a variety of sulfur- and phosphorus- or arsenic-containing metallacycles. The structurally isomeric phosphino- and arsinoarylthiols HSC6H4-2-EPh2 (ESH) combine a phosphine or arsine centre with a thiol functionality, which is usually deprotonated on coordination. These compounds have been shown to be very versatile ligands that form stable complexes with a wide range of transition metals. The heterotopic ligand 1-Ph2AsSC6H4-2-PPh2 (P,SAs) not only combines the properties of phenylthio(diphenyl)arsine and 2-diphenylphosphanylbenzenethiol by incorporating all three donor atoms in its structure, but also allows the effect of the PPh2 group in the ortho position on the cleavage of the As–S bond to be studied.

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Phosphorus–fluorine chemistry. Part XXII. Alkylthio- and arylthio-substituted fluorophosphoranes

Cited by 29 publications

References 0 publications

Preparation and nuclear magnetic resonance study of phosphorus–fluorine compounds undergoing intramolecular exchange. Part 4. Rotameric forms of 1-piperidyltrifluorophosphoranes

Preparation and nuclear magnetic resonance study of phosphorus–fluorine compounds undergoing intramolecular exchange. Part 4. Rotameric forms of 1-piperidyltrifluorophosphoranes

X−H (X=C, N, O, P, S) Bond Activations Induced byβ-Heterosubstituted Zirconaindenes

Synthesis and coordination chemistry of thiophenol-based heterodonor ligands containing P,S, As,S and P,SAs donor atoms

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