Tris(Trimethylsilyl)Phosphine and Lithium Bis(Trimethylsilyl)Phosphide.Bis‐(Tetrahydrofuran)

Becker, Gerd; Schmidt, Helmut; Uhl, G.; Uhl, Werner; Regitz, Manfred; Rösch, Wolfgang; Vogelbacher, Uwe‐Josef

doi:10.1002/9780470132586.ch48

Cited by 51 publications

(8 citation statements)

References 12 publications

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“…This highly reactive synthon is proved to be more favorable for the 1-heteroalkylation than a gaseous and toxic phosphine, PH 3 , and its derivatives, which were applied earlier (cf. [7,8]). So, we found that phosphine 1 reacted with an excess of bis(dialkylamino)methanes under heating at 80-120…”

Section: Resultsmentioning

confidence: 96%

1‐Heteroakylation of tris(trimethylsilyl)phosphine

Prishchenko

Ливанцов

Novikova

et al. 2010

Heteroatom Chemistry

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Section: Resultsmentioning

confidence: 96%

1‐Heteroakylation of tris(trimethylsilyl)phosphine

Prishchenko

Ливанцов

Novikova

et al. 2010

Heteroatom Chemistry

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“…KHMDS, 60 °C, 3 d). (iv) One pot synthesis of [Et4P]Br (15), with base (from P4: 1.6 equiv. Bu3SnH, PhMe, 455 nm LEDs, RT, 16 h, then 5 equiv.…”

Section: Discussionmentioning

confidence: 99%

“…This stands in stark contrast to other common "P 3-" synthons such as P(SiMe3)3 and represents a considerable practical advantage. 15 The precise mechanism of the P4 hydrostannylation reaction remains under investigation.…”

Section: Hydrostannylation Of P4mentioning

confidence: 99%

“…As a result, methods for the direct functionalisation of P4 remain exceedingly rare. [14][15][16][17][18][19][20][21][22][23][24] The few known examples typically require highly forcing conditions and/or undesirable reagents (such as alkali metal reductants or elaborate transition metal -even precious metal -complexes) to ensure that the reactions are driven to completion, severely limiting their scope and practicality.We describe herein a simple, efficient, 'one-pot' synthesis of various valuable and industrially relevant monophosphorus species from P4 using only commonly available reagents (Fig. 1b).…”

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confidence: 99%

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Synthesis of monophosphines directly from white phosphorus

et al. 2021

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Monophosphorus compounds are of enormous industrial importance due to the crucial roles they play in applications including pharmaceuticals, photoinitiators, and ligands for catalysis, among many others. White phosphorus (P4) is the key starting material for the preparation of all such chemicals. However, current production depends upon indirect and inefficient, multistep procedures. Here, we report a simple, effective 'one pot' synthesis of a wide range of organic and inorganic monophosphorus species directly from P4. Reduction of P4 using tri-nbutyltin hydride and subsequent treatment with various electrophiles affords compounds that are of key importance for the chemical industry, and requires only mild conditions and inexpensive, easily handled reagents. Crucially, we also demonstrate facile and efficient recycling and ultimately even catalytic use of the tributyltin reagent, thereby avoiding the formation of significant Sn-containing waste. Accessible, industrially relevant products include the fumigant PH3, the reducing agent hypophosphorous acid, and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride. Main TextWhite phosphorus (P4) is one of the most important synthetic feedstocks for the modern chemical industry, 1 and is produced on a scale of > 1 Mt per year. The pyrophoric nature of P4 and its hazardous and energy-intensive synthesis from phosphate ores have prompted recent academic efforts to bypass this compound and instead use phosphate materials directly as synthetic precursors. [2][3][4] Other researchers have emphasized the need to develop more sustainable routes for the recycling and reuse of P-containing materials, which are otherwise 2 lost as environmentally-hazardous wastes. 2,5,6 However, despite these efforts, P4 remains the only industrially-viable precursor from which to prepare the vast majority of monophosphorus compounds, which find applications ranging from pharmaceuticals to chemical catalysts. [7][8][9] Unfortunately, state-of-the-art industrial methods for the synthesis of these useful P1 species rely on indirect and correspondingly inefficient multi-step processes. The most common route (Fig. 1a) involves oxidation of P4 by toxic Cl2 gas to generate extremely corrosive PCl3. 10 Treatment with suitable nucleophiles then provides the desired products via substitution of chloride, with concomitant generation of chloride-containing waste. Alternatively, some P1 products can be generated by hydrophosphination of unsaturated organic compounds using PH3 gas. However, industrial-scale preparation of PH3 involves acid-catalysed or alkalimediated disproportionation of P4, which demands harsh reactions conditions and produces phosphorus oxyacid derivatives as stoichiometric byproducts (Figure 1). 10 Recognition of the deficiencies of current routes for generating P1 products has prompted a strong desire to discover reactions that are capable of transforming P4 into these useful compounds directly, bypassing the need for isolation and manipulation of potentially hazard...

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“…Tris(trimethylsilyl)phosphine was prepared according to a literature route. 22 All other chemicals were of reagent grade and used as supplied unless otherwise stated. The 31 P{ 1 H} NMR spectra were recorded on Jeol Eclipse 300 and Bruker DPX500 spectrometers operating at 121.7 and 202.5 MHz respectively, and referenced to 85% H 3 PO 4 (d = 0 ppm).…”

Section: Methodsmentioning

confidence: 99%

Tungsten(0) and rhodium(I) complexes of a series of 2-(2′-halo)triarylphosphinines

et al. 2009

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A series of halo substituted triarylphosphinines have been synthesised and coordinated to tungsten(0) and rhodium(I) to give [(2-(2'-halo)-triarylphosphinine)W(CO)(5)] and [(2-(2'-halo)-triarylphosphinine)Rh(COD)Cl] respectively. The complexes have been examined by NMR and IR spectroscopy in an effort to elucidate the nature of the bonding between the phosphinines and the respective metal centre. The W(CO)(5)(L) systems reveal restricted C-C bond rotation as evidenced by temperature-dependent (31)P{(1)H} NMR spectra. Thermodynamic barriers to the rotation are dependent upon the nature of the halide with DeltaG(double dagger) values of 72.5 kJ mol(-1) and 50.8 kJ mol(-1) being obtained for the chloro- and fluoro-derivatives, respectively; activation barriers for the iodo- and bromo- derivatives were beyond the accessible temperature range of the NMR experiment.

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Tris(Trimethylsilyl)Phosphine and Lithium Bis(Trimethylsilyl)Phosphide.Bis‐(Tetrahydrofuran)

Cited by 51 publications

References 12 publications

1‐Heteroakylation of tris(trimethylsilyl)phosphine

1‐Heteroakylation of tris(trimethylsilyl)phosphine

Synthesis of monophosphines directly from white phosphorus

Tungsten(0) and rhodium(I) complexes of a series of 2-(2′-halo)triarylphosphinines

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