3824-71-3

Upstream product

• 1153-05-5 triphenylarsineoxide 
• 603-32-7 triphenyl-arsane 
• 836-77-1 perfluoro-N-fluoropiperidine 

Relevant academic research and scientific papers

Complexes of molybdenum(VI) oxide tetrafluoride and molybdenum(VI) dioxide difluoride with neutral N- and O-donor ligands

[MoOF4(MeCN)], prepared from reaction of MoF6 with (Me3Si)2O in anhydrous MeCN solution, reacts with the neutral O-donor ligands, thf, Ph3PO, Me3PO, dmf and dmso, (L) in a 1:1 molar ratio u

Examining Trichloroisocyanuric Acid and Oxalyl Chloride in Complementary Approaches to Fluorination of Group 15 Heteroatoms

A mild, oxidative fluorination approach to a variety of fluorinated phosphorus compounds using trichloroisocyanuric acid (TCICA) and KF was developed as a complement to a recent study on deoxygenative fluorination using oxalyl chloride. Herein, the syntheses of several fluorinated organophosphorus compounds are reported, and both TCICA/KF and oxalyl chloride/KF conditions are compared and contrasted throughout. Initial investigations of the method on other group 15 heteroatoms (i. e., As, Sb, and Bi) are also reported, with varied success. This work notably extends the known TCICA/KF reactivity series to another group of elements beyond previously studied chalcogens (S, Se, and Te) and halogens (iodine) and expands the utility of the previously reported oxalyl chloride/KF method.

Deoxygenative Fluorination of Phosphine Oxides: A General Route to Fluorinated Organophosphorus(V) Compounds and Beyond

Fluorinated organophosphorus(V) compounds are a very versatile class of compounds, but the synthetic methods available to make them bear the disadvantages of 1) occasional handling of toxic or pyrophoric PIII starting materials and 2) a dependence on hazardous fluorinating reagents such as XeF2. Herein, we present a simple solution and introduce a deoxygenative fluorination (DOF) approach that utilizes easy-to-handle phosphine oxides as starting materials and effectively replaces harsh fluorinating reagents by a combination of oxalyl chloride and potassium fluoride. The reaction has proven to be general, as R3PF2, R2PF3, and RPF4 compounds (as well as various cations and anions derived from these) are accessible in good yields and on up to a multi-gram scale. DFT calculations were used to bolster our observations. Notably, the discovery of this new method led to a convenient synthesis of 1) new difluorophosphonium ions, 2) hexafluorophosphate salts, and 3) fluorinated antimony- and arsenic- compounds.

Unusual neutral ligand coordination to arsenic and antimony trifluoride

The preparations and spectroscopic characterisation of the hydrolytically unstable As(iii) complexes, [AsF3(OPR3)2] (R = Me or Ph) and [AsF3{Me2P(O)CH2P(O)Me 2}] are described and represent the first examples of complexes of AsF3 with neutral ligands. The crystal structure of [AsF 3{Me2P(O)CH2P(O)Me2}] contains dimers with bridging diphosphine dioxide, but there are also long contacts between the dimers to neighbouring phosphine oxide groups, completing a very distorted six-coordination at arsenic and producing a weakly associated polymer structure. The reaction of AsF3 with OAsPh3 affords Ph3AsF2, and no arsine oxide complex was formed. Reaction of SbF3 with OER3 (R = Me or Ph, E = P or As), Me 2P(O)CH2P(O)Me2 and Ph2P(O)(CH 2)nP(O)Ph2 (n = 1 or 2) in MeOH produces [SbF3(OER3)2], [SbF3{Me 2P(O)CH2P(O)Me2}] and [SbF3{Ph 2P(O)(CH2)nP(O)Ph2}] respectively. The X-ray structures reveal that the complexes contain square pyramidal SbF 3O2 cores with apical F and cis disposed pnictogen oxides. However, whilst [SbF3(OER3)2] (R = Ph: E = P or As; R = Me: E = As) and [SbF3{Ph2P(O)CH 2P(O)Ph2}] are monomeric, [SbF3{Me 2P(O)CH2P(O)Me2}] is a dimer with bridging diphosphine dioxides producing a twelve-membered ring, and [SbF 3{Ph2P(O)(CH2)2P(O)Ph2}] is a chain polymer with diphosphine dioxide bridges. In the OAsR3 reactions with SbF3, R3AsF2 are also formed. Notably the Sb-O(P) bonds are shorter than As-O(P), despite the covalent radii (As 3. IR and multinuclear (1H, 19F and 31P) NMR data are reported and discussed. BiF3 does not react with pnictogen oxide ligands under similar conditions and halide exchange of bismuth chloro complexes with Me3SnF gave BiF3.

Persistent perfluoroalkyl radical investigations under reductive environment: Reaction with electron-donating reagents

The reactivity of persistent perfluoroalkyl radical, perfluoro-3-ethyl-2,4-dimethyl-3-pentyl (1), with various electron-donating reagents was investigated. It is revealed that 1 which is robust under oxidative conditions is rather vulnerable under reductive conditions. Thus, Lewis bases such as triethylamine and triphenylpnictogens (Ph3Pn, Pn=N, P, As, Sb, Bi) and some soft anions such as iodide or tetraphenyl borate reacted with 1 to give perfluoro-3-isopropyl-4-methylpent-2-ene (2) quantitatively. Even very weak Lewis bases such as diethyl ether and diethylsulfide also reacted with 1 to give 2 and additionally a hydrido product, perfluoro-3-ethyl-3-H-2,4-dimethylpentane (4). Hydrogen gas did not react with 1 at all without a catalyst, but in the presence of metal Pd adsorbed on charcoal, smoothly reacted to give 2 in quantitative yield. Metal hydrides such as LiAlH4, NaBH4, NaH, BH3 (THF complex), Bu3SnH, Me2PhSiH reacted with 1 to give 2 and 4. That an electron transfer mechanism is operating in the formation of 2 is obvious, but not conclusive in the formation of 4.

FLUORINATION WITH POSITIVE FLUORINE GENERATED FROM ISOELECTRONICALLY RELATED REAGENTS

Compounds such as PhIF2, PhPF2 and XeF2, which have been used previously as unrelated fluorinating agents, are shown to be periodically related as isoelectronic molecules E3AF2 of trigonal-bipyramidal shape, where E represents a bonded or nonbonded electron pair and A a main Group V-VIII element.These compounds are arranged in order of halogenating ability by estimating the magnitude of reduction couples, approximated by ΔH0f(E3AF2-E3A), or by noting the direction of redox reactions involving the couples.The A sequence deduced Kr>Xe ca.Cl>Br>I>S>Se>Te-As-Sb>P agrees with the limited experimental data available.Evidence for an ionic mechanism involving 'onium' monohalide ions is given for halogenations with these reagents when carried out under "Friedel-Crafts" conditions although no stable salts containing these ions have as yet been isolated because of intramolecular halogenation.These ions act as sources of positive fluorine.The use of ring deactivated reagents to achieve halogenation is discussed.

REACTIONS OF TRIPHENYLARSINE OXIDE WITH AQUEOUS HYDROGEN FLUORIDE: CRYSTAL STRUCTURE OF BIS(TRIPHENYLARSINE OXIDE)HYDROGEN(I) TETRAFLUOROBORATE

Fluorination of triphenylarsine oxide by aqueous hydrogen fluoride (1-40percent) in the absence of glass readily gives triphenylarsine difluoride.When the reaction with dilute (1percent) aqueous hydrogen fluoride is carried out in borosilicate glass apparatus, the glass participates in the reaction resulting in the formation of the crystalline 2:1 adduct 2Ph3AsO*HBF4.Crystals of this compound are monoclinic, P21/c, a = 12.926(4), b = 17.819(6), c = 14.994(4) Angstroem, β = 98.97(3) deg, Z = 4.The structure contains cations (1+) in which O....O is 2.44(2) Angstroem, and anions BF4-.