2359-99-1

Upstream product

• 16523-54-9 chlorodicyclohexylphosphane 
• 829-85-6 diphenylphosphane 
• 2844-89-5 dichlorocyclohexylphosphine 
• 70530-88-0 Chlor-diethylamino-cyclohexyl-phosphan 
• 108-85-0 1-bromocyclohexane 
• 1402214-57-6 CF₃O₃S^(1-)*C₂₉H₅₁N₂P₄⁽¹⁺⁾ 
• 75-05-8 acetonitrile 
• 73930-97-9 3-acetoxy-1,3-diphenylpropene 
• 829-84-5 dicyclohexylphosphane 
• 931-51-1 cyclohexylmagnesiumchloride 
• 106-93-4 ethylene dibromide 
• 107-06-2 1,2-dichloro-ethane 
• 83115-12-2 (2,4,6-tri-tert-butylphenyl)phosphine 
• 83438-72-6 bis(chloro)phosphorane 

Downstream Products

• 131028-86-9 Bis-<2,2-dicyclohexyl-4,5-(tetrachlorbenzo)-1,3,2λ⁵-dioxaphospholen-2-yl>-1,2-dioxatetrachlorphenylen 
• 105185-97-5 {HgI₂(C₂₄H₄₄P₂)} 
• 105186-00-3 di-iodo-tetracyclohexyldiphosphine-cobalt(II) 
• 105092-53-3 di-bromo-tetracyclohexyldiphosphine-cobalt(II) 
• 105092-53-3 di-bromo-tetracyclohexyldiphosphine-cobalt(II) 
• 105185-98-6 di-chloro-tetracyclohexyldiphosphine-cobalt(II) 
• 119721-08-3 tetracyclohexyl-diphosphane-P,P'-dioxide 
• 109019-49-0 dicyclohexylphosphinous iodide 
• 100384-03-0 dicyclohexylbromophosphine 
• 3676-98-0 tetracyclohexyl-diphosphane-P,P'-disulfide 

Relevant academic research and scientific papers

Controlled scrambling reactions to polyphosphanes: Via bond metathesis reactions

Triphosphanes R′2PP(R)PR′2 (9a,c: R = Py; 9b R = BTz), 1,3-diphenyl-2-pyridyl-triphospholane 9d and pentaphospholanes (RP)5 (13: R = Py; 18: R = BTz) are obtained in high yield of up to 98% from the reaction of dipyrazolylphosphanes RPpyr2 (5: R = Py; 6: R = BTz; pyr = 1,3-dimethylpyrazolyl) and the respective secondary phosphane (R′2PH, R′ = Cy (9a,b), tBu (9c); PhPH(CH2)2PHPh (9d)). The formation of derivatives 9a-d proceeds via a condensation reaction while the formation of 13 and 18 can only be explained by a selective scrambling reaction. We realized that the reaction outcome is strongly solvent dependent as outlined by the controlled scrambling reaction pathway towards pentaphospholane 13. In our further investigations to apply these compounds as ligands we first confined ourselves to the coordination chemistry of triphosphane 9a with respect to coinage metal salts and discussed the observation of different syn- and anti-isomeric metal complexes based on NMR and X-ray analyses as well as quantum chemical calculations. Methylation reactions of 9a with MeOTf yield triphosphan-1-ium Cy2MePP(Py)PCy2+ (10+) and triphosphane-1,3-diium Cy2MePP(Py)PMeCy22+ (112+) cations as triflate salts. Salt 11[OTf]2 reacts with pentaphospholane 13 in an unprecedented chain growth reaction to give the tetraphosphane-1,4-diium triflate salt Cy2MePP(Py)P(Py)PMeCy22+ (19[OTf]2) via a P-P/P-P bond metathesis reaction. The latter salt is unstable in solution and rearranges via a rare [1,2]-migration of the Cy2MeP-group followed by the elimination of the triphosph-2-en-1-ium cation [Cy2MePPPMeCy2]+ (20+) to yield a novel 1,4,2-diazaphospholium salt (21[OTf]).

Bismuth Amides Mediate Facile and Highly Selective Pn–Pn Radical-Coupling Reactions (Pn=N, P, As)

The controlled release of well-defined radical species under mild conditions for subsequent use in selective reactions is an important and challenging task in synthetic chemistry. We show here that simple bismuth amide species [Bi(NAr2)3] readily release aminyl radicals [NAr2]. at ambient temperature in solution. These reactions yield the corresponding hydrazines, Ar2N?NAr2, as a result of highly selective N?N coupling. The exploitation of facile homolytic Bi?Pn bond cleavage for Pn?Pn bond formation was extended to higher homologues of the pnictogens (Pn=N–As): homoleptic bismuth amides mediate the highly selective dehydrocoupling of HPnR2 to give R2Pn?PnR2. Analyses by NMR and EPR spectroscopy, single-crystal X-ray diffraction, and DFT calculations reveal low Bi?N homolytic bond-dissociation energies, suggest radical coupling in the coordination sphere of bismuth, and reveal electronic and steric parameters as effective tools to control these reactions.

Room-temperature reduction of sulfur hexafluoride with metal phosphides

Upon treatment with sulfur hexafluoride, alkali metal diphenyl or dicyclohexyl phosphides are oxidized within seconds to tetraphenyl or tetracyclohexyl diphosphines. When bulky di-tert-butylphosphide is employed, fluorophosphine intermediates are detected. This is the first reported reaction of sulfur hexafluoride with metal phosphides, and a rare example of reactivity of sulfur hexafluoride at ambient temperature. This journal is

Evidence for Iron-Catalyzed α-Phosphinidene Elimination with Phenylphosphine

The ubiquitous half-sandwich iron complex [CpFe(CO)2Me] (Cp=η5-C5H5) appears to be a catalyst for α-phosphinidene elimination from primary phosphines. Dehydrocoupling reactions provided initial insight into this unusual reaction mechanism, and trapping reactions with organic substrates gave products consistent with an α elimination mechanism, including a rare example of a three-component reaction. The substrate scope of this reaction is consistent with generation of a triplet phosphinidene. In all, this study presents catalytic phosphinidene transfer to unsaturated organic substrates.

Cationic 5-phosphonio-substituted N-heterocyclic carbenes

2-Phosphanyl-substituted imidazolium salts 2-PR2(4,5-Cl-Im)[OTf] (9a,b[OTf]) (4,5-Cl-Im = 4,5-dichloro-1,3-bis(2,6-di-isopropylphenyl)-imidazolium) (a: R = Cy, b: R = Ph) are prepared from the reaction of R2PCl (R = Cy, Ph) with NHC 8 (4,5-dichloro-1,3-bis(2,6-di-isopropylphenyl)-imidazolin-2-ylidene) in the presence of Me3SiOTf. 5-Phospanyl-substituted imidazolium salts 5-PR2(2,4-Cl-Im)[OTf] (10a,b[OTf]) are obtained in quantitative yield when a slight excess of the NHC 8 is used. 5-Phosphonio-substituted imidazolium salts 5-PR2Me(2,4-Cl-Im)[OTf]2 (14a,b[OTf]2) and 5-PR2F(2,4-Cl-Im)[OTf]2 (16a,b[OTf]2) result from methylation reaction or oxidation of 10a,b[OTf] with XeF2 and subsequent fluoride abstraction. According to our quantum chemical studies the Cl1 atom at the 2-position at the imidazolium ring of dication 14b2+ carries a slightly positive charge and is therefore accessible for nucleophilic attack. Accordingly, the reaction of 14a,b[OTf]2 and 16a,b[OTf]2 with R3P (R = Cy, Ph) affords cationic 5-phosphonio-substituted NHCs 5-PR2Me(4-Cl-NHC)[OTf] (17a,b[OTf]) and 5-PR2F(4-Cl-NHC)[OTf] (18a,b[OTf]) via a SN2(Cl)-type reaction. A series of transition metal complexes such as [AuCl(5-PPh2Me(4-Cl-NHC))][OTf] (19[OTf]), [CuBr(5-PPh2Me(4-Cl-NHC))][OTf] (20[OTf]), [AuCl(5-PPh2F(4-Cl-NHC))[OTf] (21[OTf]) and [RhCl(cod)(5-PPh2Me(4-Cl-NHC))][OTf] (23[OTf]) are prepared to prove the coordination abilities of carbenes 17b[OTf] and 18b[OTf]. The isolation of a rare example of a tricationic bis-carbene silver complex [Ag(5-PPh2Me(4-Cl-NHC))2][OTf]3 (22[OTf]3) is achieved by reacting 14b[OTf] with Cy3P in the presence of AgOTf. NHC 17b[OTf] represents a very effective dehydrocoupling reagent for secondary (R2PH, R = Ph, Cy, iBu) and primary (RPH2, R = Ph, Cy) phosphanes to give diphosphanes of type R4P2 (R = Ph, Cy, iBu) and oligophosphanes R4P4, R5P5 (R = Ph, Cy), respectively. Methylation of 17b+ and subsequent deprotonation reaction with LDA affords the cationic NHO (N-heterocyclic olefin) 35+ of which the gold complex 36+ is readily accessible via the reaction with AuCl(tht).

Facile, Catalytic Dehydrocoupling of Phosphines Using β-Diketiminate Iron(II) Complexes

Catalytic dehydrocoupling of primary and secondary phosphines has been achieved for the first time using an iron pre-catalyst. The reaction proceeds under mild reaction conditions and is successful with a range of diarylphosphines. A proton acceptor is not needed for the transformation to take place, but addition of 1-hexene does allow for turnover at 50°C. The catalytic system developed also facilitates the dehydrocoupling of phenylphosphane and dicyclohexylphosphane. A change in solvent switches off dehydrocoupling to allow hydrophosphination of alkenes.

Exploration of tin-catalyzed phosphine dehydrocoupling: Catalyst effects and observation of tin-catalyzed hydrophosphination

The phosphine substrate scope in dehydrocoupling reactions catalyzed by Cp?2SnCl2 (Cp? = pentamethylcyclopentadienyl, 1) have been explored. Catalyst variants R2SnX2 (R = Cp?, Ph; X = Cl, Me, Ph) were also tested, which revealed that activity is dependent on the Cp? ligands as well as more electron withdrawing X ligands. Steric factors at the phosphine substrate are also important. Compound 1 was found to be a catalyst for hydrophosphination of styrene, 2,3-dimethylbutadiene, and diphenylacetylene with phenylphosphine, which is the first example of a p-block catalyst for hydrophosphination.

One-pot syntheses of cationic polyphosphorus frameworks with two-, three-, and four-coordinate phosphorus atoms by one-pot multiple P-P bond formations from a P1 source

Accessible complexity: Polyphosphorus frameworks [R4P 4pyr]+ and [R6P7]+ (R=Cy, Ph; pyr=3,5-dimethylpyrazolyl) were prepared from a P1 source, R2PH. In a one-pot reaction, eight P-P bonds are formed via a unique combination of substitution and base-induced reductive P-P coupling. Copyright

Radical synthesis of trialkyl, triaryl, trisilyl and tristannyl phosphines from P4

A reaction scheme has been devised according to 3 RX + 3 Ti(iii) + 0.25 P4 → PR3 + 3 XTi(iv), wherein RX = PhBr, CyBr, Me3SiI or Ph3SnCl, with contrasting results in the case of more hindered RX. The scheme accomplishes the direct radical functionalization of white phosphorus without the intermediacy of PCl3.

Remarkable product diversity in the "self-organized" reaction of deprotonated acetonitrile with chlorophosphines

This study examined the reaction of in situ deprotonated acetonitrile with different chlorophosphines ClPR2 (5a-d) to find new nitrile functionalized bis(diphenylphosphino)methane (dppm) ligands. Depending on the steric and electronic demand of