Tri-<i>n</i>-butylstannane

RajanBabu, T. V.; Page, Philip C. Bulman; Buckley, Benjamin R.

doi:10.1002/047084289x.rt181

Cited by 2 publications

(3 citation statements)

References 154 publications

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“…To make use of the transient formation, thermal reactions of P -nitroxyl complex 1 with various group 14 hydrides R 3 EH (E = Si, Ge, Sn) were investigated. First, we examined the case of tri- n -butylstannane on the basis of the ability of the transiently formed tri- n -butylstannyl radical to act as an effective trap for (other) radical species (Scheme ).…”

Section: Results and Discussionmentioning

confidence: 99%

Chemistry of Thermally Generated Transient Phosphanoxyl Complexes

Heurich

Schnakenburg

et al. 2017

Organometallics

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Investigations on the reactivity of the transiently formed phosphanoxyl complex [(CO) 5 W(Ph 2 PO • )], thermally generated from [(CO) 5 W(Ph 2 PO-TEMP)] in toluene, is presented. Apart from self-reactions, trapping of this radical complex was achieved using group 14 hydrides Ph 3 EH (E = Si, Ge, Sn), leading to new phosphane complexes possessing a P−O−EPh 3 bonding motif and the corresponding TEMP-H as byproduct. Reaction pathways, derived from DFT calculations, clearly revealed the intermediacy of various openshell complexes; EPR measurements showed the presence of radicals, but unfortunately interpretation was not achieved.

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Section: Results and Discussionmentioning

confidence: 99%

Chemistry of Thermally Generated Transient Phosphanoxyl Complexes

Heurich

Schnakenburg

et al. 2017

Organometallics

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“…[17][18][19][20][21][22] We reasoned that the inexpensive, commercially available radical source Bu3SnH could serve as a convenient reagent for breaking apart the P4 molecule, since Bu3SnH readily generates formal H• and Bu3Sn• radicals upon photolysis or thermolysis in the presence of a radical initiator. [31][32][33][34] In an initial experiment, Bu3SnH and P4 were combined in a 6:1 molar ratio in PhMe at room temperature. Gratifyingly, 31 P{ 1 H} NMR spectroscopic monitoring of the mixture showed clear consumption of P4 over the course of several days, with concomitant appearance of new upfield resonances at −288.7 and −324.9 ppm (major), and −242.0 and −346.4 ppm (trace), which collectively correspond to the products (Bu3Sn)nPH3-n (n = 0-3, vide infra).…”

Section: Hydrostannylation Of P4mentioning

confidence: 99%

“…Nevertheless, the use of light as an initiator clearly suggests a radical process, as radical chain reactions mediated by Bu3SnH are well established. [31][32][33][34] A plausible mechanism is therefore outlined in Fig. 2b, in which each P-P bond is cleaved through initial attack of a Bu3Sn‧ radical (for example, generated by photoelectron catalysis; Supplementary Method 1), [40][41][42] followed by abstraction of H‧ by the resulting P-centred radical from another equivalent of Bu3SnH, to regenerate Bu3Sn‧ and continue the radical chain.…”

Section: Hydrostannylation Of P4mentioning

confidence: 99%

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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Tri-n-butylstannane

Cited by 2 publications

References 154 publications

Chemistry of Thermally Generated Transient Phosphanoxyl Complexes

Chemistry of Thermally Generated Transient Phosphanoxyl Complexes

Synthesis of monophosphines directly from white phosphorus

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