1101-41-3Relevant academic research and scientific papers
A study of the reactivity of secondary phosphanes with radical sources: A new dehydrocoupling reaction
Baker, Robert J.,Hashem, Emtithal
, p. 1081 - 1085 (2010)
The reactions of secondary phosphanes with radical sources have been investigated.Astoichiometric dehydrocoupling of Ph2PH with 1,1′-azobis[cyclohexane-1-carbonitrile] (VAZO 88) affords tetraphenyldiphosphane in good yields, whilst reduction of the nitrosyl function was observed upon using 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO). Dialkylphosphane - borane adducts also undergo a dehydrocoupling reaction in the presence of VAZO 88 to form R4P2.
ZUR DISPROPORTIONIERUNG DER PHENYLFLUOROPHOSPHANE (C6H5)2PF UND (C6H5)PF2
Riesel, L.,Haenel, J.,Ohms, G.
, p. 335 - 340 (1988)
Ph2P-PF2Ph2 has been identified by means of 19F- and 31P-NMR spectroscopy as an intermediate product of the disproportionation of Ph2PF.The disproportionation is catalyzed by acids.The reaction mechanism is discussed.PhPF2 disproportionates faster in solution inacetonitrile that neat, forming (PhP)6, instead of (PhP)5.
SYNTHESIS AND COORDINATING PROPERTIES OF (o-DIPHENYLPHOSPHINOBENZYL)DIMETHYLSILANE
Ang, H. G.,Lau, P. T.
, p. 285 - 292 (1985)
The reactions of (o-diphenylphosphinobenzyl)dimethylsilane with manganese and rhenium carbonyl afford o-(C6H5)2PC6H4CH2Si(CH3)2M(CO)4 (M=Mn, Re), in which the ligand behaves as a chelate.Similar reactions occur with ?-cyclopentadienemolybdenum tricarbonyl dimer to give o-(C6H5)2PC6H4CH2Si(CH3)2Mo(?-C5H5)(CO)2.However, photolysis of a mixture of the ligand with manganese carbonyl yielded o-(C6H5)2PC6H4CH2Si(H)(CH3)2Mn2(CO)9.
Phosphinomethanides and group 15 element halides: Redox reactions, rearrangements and novel heterocycles
Karsch,Witt
, p. 151 - 169 (1997)
The reactions of ECl3 (E = P, As, Sb, Bi), RPCl2 (R = Me, Ph, 1Bu, Cy2N) and Ph2PCl, respectively, with ambident lithium phosphinomethanides are described. The reaction with LiCH2PMe2, 1, by E-C bond formation, leads to the substitution products E(CH2PMe2)3, 2a-d, (E = P, As, Sb, Bi) and R-P(CH2PMe2)2 (R = Me, Ph, 1Bu, Cy2N) 5a-d. In contrast, LiC(PMe2)(SiMe3)2 -0.5TMEDA, 6, gives substitution products with ECl3 (E = P, As, Sb), by E-P bond formation. Thus, the first element-tris(P-ylide)derivatives E(PMe2=C(SiMe3)2)3, 7a-c, are obtained. 7b is characterized by X-ray structure determination. In these reactions, oxidative P-P coupling to give [(Me3Si)2C=PMe2]2, 8, is also observed, and exclusively in the reaction of BiCl3 with 6. The reaction of RPCl2 (R = Me, Ph, 1Bu, Cy2N) with 6 strongly is dependent on the nature of R. For R = Me, only substitution is observed, yielding Me-P(PMe2=C(SiMe3)2)2, 10, while for R = Ph, both substitution and Li/Cl exchange with subsequent formation of 8 and the diphosphane [(Me3Si)2C=PMe2-PPh]2, 12, are found. The latter has been characterized structurally. In contrast, for R = 1Bu, only (1BuP)3, 13, and (1BuP)4, 14, are obtained. An analogous result is observed in the reaction of 1BuPCl2 with LiC(PMe2)2(SiMe3), 17. The reaction of Cy2NPCl2 with two equivalents of LiC(PMe2)(SiMe3)2 · 0.5TMEDA, 6, gives a phospha-alkene Cy2N-P=C(SiMe3)2, 16, and the substitution product Cy2N-P(PMe2=C(SiMe3)2)2, 15. Likewise, LiC(PMe2)2(SiMe3), 17, reacts with PhPCl2 to give the substitution product Ph-P(PMe2=C(PMe2)(SiMe3))2, 18, which is characterized by X-ray structure determination, whereas with MePCl2 only the P-ylide Me2P-PMe2=C(PMe2)(SiMe3), 20, and the coupling product [(Me2P)(Me3Si)C=PMe2]2, 19, are formed. The latter is also obtained in the reactions of BiCl3 or SbCl3 with LiC(PMe2)2(SiMe3), 17. Analogous redox reactions with AsCl3 and PCl3, respectively, lead to the bis-pentacyclic {μ-[C(PMe2)2(SiMe3)]As2}2, 21, and the hexacycle P-PMe2-C(SiMe3)-PMe2-C(SiMe3)-PMe2, 22, which were structurally characterized by X-ray analyses. Depending on the reaction conditions, the reaction of PCl3 with LiC(PMe2)2(SiMe3), 17, alternatively may lead to the triphosphete P-PMe2-C(SiMe3)-PMe2, 24. By using P-phenyl-substituents instead of P-methyl-substituents, i.e. in the reaction of LiC(PPh2)2(SiMe3), 25, with PCl3 or AsCl3, the triphosphete P-PPh2-C(SiMe3)-PPh2, 26a, or its arsenic analogue As-PPh2-C(SiMe3)-PPh2, 26b, are respectively formed, along with the chlorine substituted ylide (Cl)(Ph)2P=C(PPh2)(SiMe3), 27. 26a,b are characterized by X-ray structure determinations. The synthesis of the first ten-electron phosphorus cation P[C(PPh2)2(SiMe3)]+2, 30, with a homonuclear, spirocyclic PP4-framework was achieved by reacting the triphosphete 26a with the ylide 27 in the presence of NaBPh4. The crystal structure of the cation of 30, which adopts a Ψ-tbp geometry, was determined.
Reactions of Low-Coordinate Cobalt(0)-N-Heterocyclic Carbene Complexes with Primary Aryl Phosphines
Wang, Dongyang,Chen, Qi,Leng, Xuebing,Deng, Liang
, p. 15600 - 15609 (2018)
Aiming to get knowledge on the reactivity of low-coordinate cobalt(0) species toward primary phosphines, the reactions of [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] (IPr = 1,3-bis(2′,6′-diisopropylphenyl)imidazol-2-ylidene, ICy = 1,3-dicyclohexylimidazol-2-ylidene, and vtms = vinyltrimethylsilane) with several primary aryl phosphines have been examined. The reactions of [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] with H2PDmp (Dmp = 2,6-dimesitylphenyl) at 80 °C furnish the diamagnetic cobalt(I) phosphido complexes [(NHC)Co(PHDmp)] (NHC = IPr, 1; ICy, 2) that feature the Co-(η6-mesityl) interaction. Complex 1 can coordinate CO to generate the terminal phosphido complex [(IPr)Co(CO)3(PHDmp)] (3) and can be oxidized by [Cp2Fe][BArF4] to yield the cobalt(II) phosphido complex [(IPr)Co(PHDmp)][BArF4] (4, BArF4 = tetrakis(3,5-di(trifluoromethyl)phenyl)borate). For the reactions with sterically less-hindered primary phosphines, [(IPr)Co(vtms)2] is inert toward H2PC6H2-2,4,6-Me3 (H2PMes) at room temperature, whereas [(ICy)2Co(vtms)] can react with H2PMes at room temperature to produce the cobalt(II) phosphido alkyl complex trans-[(ICy)2Co(CH2CH2SiMe3)(PHMes)] (5). At 80 °C, the cobalt(0) alkene complexes [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] and also the cobalt phosphido complexes, 1, 2, and 5 can serve as precatalysts for the dehydrocoupling reaction of H2PMes to afford MesHPPHMes. NHC-Co(I)-phosphido species are proposed as the in-cycle intermediates for these cobalt-catalyzed dehydrocoupling reactions.
Phosphanylphosphido and phosphanylphosphinidene complexes of zirconium(IV) supported by bidentate N,N ligands
Zauliczny, Mateusz,Grubba, Rafa?,Ponikiewski, ?ukasz,Pikies, Jerzy
, p. 353 - 360 (2017)
Phosphanylphosphido complexes of zirconium, [NacNacZrCl2(η2-R2P–PSiMe3)] (R?=?t-Bu, i-Pr), were synthesized in the reaction of R2P–P(SiMe3)Li·nTHF (R?=?t-Bu, i-Pr) with a β-diketiminate complex, [NacNacZrCl3], in toluene. Elimination of Me3SiCl from [NacNacZrCl2(η2-R2P–PSiMe3)] provided the phosphanylphosphinidene complexes [NacNacZrCl(η2-R2P–P)] (R?=?t-Bu, i-Pr). Moreover, the reaction of [NacNacZrCl2(η2-R2P–PSiMe3)] with R2P–P(SiMe3)Li·nTHF yielded the phosphanylphosphinidenoid complexes [NacNacZrCl2(η2-R2P–PLi)] (R?=?t-Bu, i-Pr). The same reaction, but in the presence of 12-crown-4, gave rise to the phosphanylphosphinidene complexes [NacNacZrCl(η2-R2P–P)]. The X-ray structures of [NacNacZrCl2(η2-i-Pr2P–PSiMe3)] and [NacNacZrCl(η2-t-Bu2P–P)] revealed that the R2P-P ligands exhibit side-on coordination to the metal center. From the reaction of i-Pr2P–P(SiMe3)Li·3THF with [{PhN(CH2)3NPh)}ZrCl2], a triple-core, anionic, phosphanylphosphinidene complex, [{PhN(CH2)3NPh)}Zr3Cl2(μ2-Cl)(μ2-i-Pr2P–P)2(μ3-i-Pr2P–P)2]?[Li(DME)3]+, was obtained in which the i-Pr2P–P ligands exhibit bridging coordination.
Radical synthesis of trialkyl, triaryl, trisilyl and tristannyl phosphines from P4
Cossairt, Brandi M.,Cummins, Christopher C.
, p. 1533 - 1536 (2010)
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.
Calcium-centred phosphine oxide reactivity: P-C metathesis, reduction and P-P coupling
Hill, Michael S.,Mahon, Mary F.,Robinson, Thomas P.
, p. 2498 - 2500 (2010)
Reactions of triphenylphosphine oxide and diphenylphosphine oxide with calcium alkyls and amides in the presence of PhSiH3 occur to give P-C bond cleavage, P(v) to P(iii) reduction and P-P coupling. The Royal Society of Chemistry.
Metal-free Lewis acid mediated dehydrocoupling of phosphines and concurrent hydrogenation
Dobrovetsky, Roman,Takeuchi, Katsuhiko,Stephan, Douglas W.
, p. 2396 - 2398 (2015)
The stoichiometric reaction of trityl cation with two equivalents of Ph2PH affords the phosphine stabilized phosphenium salt [Ph2(H)PPPh2][B(C6F5)4] via hydride abstraction, while catalytic amounts of B(p-HC6F4)3 effects catalytic phosphine dehydrocoupling with the liberation of H2. This reaction is accelerated by the presence of olefin or imine, effecting concurrent hydrogenation.
Reactions of [Cp2Ti(η2-Me3SiC2SiMe3)] with 1,4-Bis(diphenylphosphanyl)but-2-yne: Coupling and Isomerization versus Phosphorylation
Altenburger, Kai,Rei?, Fabian,Schubert, Kathleen,Baumann, Wolfgang,Spannenberg, Anke,Arndt, Perdita,Rosenthal, Uwe
, p. 1709 - 1715 (2015)
The reactions of [Cp2Ti(η2-Me3SiC2SiMe3)] (1; Cp = η5-cyclopentadienyl) with 1,4-bis(diphenylphosphanyl)but-2-yne (2) have been investigated and found to yield a mixture of products. From these, through the coupling of 2, the tetrasubstituted titanacyclopentadiene [Cp2Ti(CCH2PPh2)4] (3) was isolated. In addition, small amounts of very unusual complexes were obtained and characterized. In one case, the substrate 2 isomerized to the allene Ph2PC(H)=C=C(H)CH2PPh2, which formed the complex [Cp2Ti{η3-Ph2PC(H)=C=C(H)CH2PPh2}] (4) through the coordination of a double bond and one of the phosphorus atoms. Another complex, [Cp2Ti{-C(CH2PPh2)=C(CH2PPh2)P(Ph2)H-}] (5), was identified to be the result of a formal hydrophosphorylation of the substrate 2 by HPPh2, and features a Ti-H-P bridge. It is not clear how HPPh2 was formed. One possible explanation is the dehydrophosphorylation of the substrate with the formation of HPPh2 and the butatriene H2C=C=C=C(H)PPh2 [tautomer of the but-2-en-3-yne HC≡C-CH=C(H)PPh2]. The molecular structures of complexes 4 and 5 were determined by X-ray analysis.
