- A Tricyclic Hexaphosphane
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The reaction of the functionalized cyclo-tetraphosphane [ClP(μ-PMes)]2 (Mes=2,4,6-tri-tert-butylphenyl) with different Lewis bases led to the formation of an unprecedented tricyclic hexaphosphane, MesP6Mes. The formation of this comp
- Bresien, Jonas,Schulz, Axel,Villinger, Alexander
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- Low temperature isolation of a dinuclear silver complex of the cyclotetraphosphane [ClP(μ-PMes?)]2
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The reaction of the cyclotetraphosphane [ClP(μ-PMes?)]2 (1, Mes? = 2,4,6-tri-tert-butylphenyl) with Ag[Al(ORF)4] (RF = CH(CF3)2) resulted in a labile, dinuclear silver complex of 1, which e
- Bresien, Jonas,Schulz, Axel,Villinger, Alexander
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- Low-temperature isolation of the bicyclic phosphinophosphonium salt [Mes?2P4Cl][GaCl4]
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The reaction of [ClP(μ-PMes?)]2 (1) with the Lewis acid GaCl3 yielded a hitherto unknown tetraphosphabicyclo[1.1.0]butan-2-ium salt, [Mes?P4(Cl)Mes?][GaCl4] (3[GaCl4]), which incorporates a positively
- Bresien, Jonas,Faust, Kirill,Schulz, Axel,Villinger, Alexander
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- Reactivity of phospha-Wittig reagents towards NHCs and NHOs
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Phospha-Wittig reagents, RPPMe3(R = Mes* 2,4,6-tBu3-C6H2;MesTer 2,6-(2,4,6-Me3C6H2)-C6H3;DipTer 2,6-(2,6-iPr2C6H
- Gupta, Priyanka,Siewert, Jan-Erik,Wellnitz, Tim,Fischer, Malte,Baumann, Wolgang,Beweries, Torsten,Hering-Junghans, Christian
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p. 1838 - 1844
(2021/02/16)
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- 3H-Phosphaallenes Revisited: Facile Synthesis by Hydroalumination of Alkynylphosphines and β-Elimination, Stability and Trapping of Transient Species by Coordination to Transition Metal Atoms
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A facile method for the efficient synthesis of 3H-phosphaallenes, R?P=C=C(H)?R′, is presented, which comprises treatment of dialkynylphosphines with dialkylaluminium hydrides (hydroalumination) and elimination of aluminium alkynides from intermediate alke
- Kl?cker, Hans,Tendyck, Jonas C.,Keweloh, Lukas,Hepp, Alexander,Uhl, Werner
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p. 4793 - 4807
(2019/03/13)
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- Dichloro-Cycloazatriphosphane: The Missing Link between N2P2 and P4 Ring Systems in the Systematic Development of NP Chemistry
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A dichloro-cycloazatriphosphane that incorporates a cyclic NP3 backbone could be synthesized using knowledge gained from the chemistry of N2P2 and P4 ring systems. It fills the gap between the congeneric compounds [ClP(μ-NR)]2 and [ClP(μ-PR)]2 (R=sterically demanding substituent), and thus contributes to the systematic development of nitrogen–phosphorus chemistry in general. The title compound was studied with respect to its formation via a labile aminodiphosphene, which readily underwent different rearrangement reactions depending on the solvent. All compounds were fully characterized by experimental and computational methods.
- Bresien, Jonas,Hinz, Alexander,Schulz, Axel,Suhrbier, Tim,Thomas, Max,Villinger, Alexander
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p. 14738 - 14742
(2017/10/12)
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- Functional small-molecules & polymers containing P=C and As=C bonds as hybrid π-conjugated materials
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Stable phospha- and arsaalkenes were used to synthesize polymers containing unsaturated P=C and As=C moieties. The composition, chemical environment, structure, optical, and electronic properties of the monomers and polymers were elucidated. The incorpora
- Morales Salazar, Daniel,Mijangos, Edgar,Pullen, Sonja,Gao, Ming,Orthaber, Andreas
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supporting information
p. 1120 - 1123
(2017/02/05)
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- A hydroboration route to geminal P/B frustrated Lewis pairs with a bulky secondary phosphane component and their reaction with carbon dioxide
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The secondary aryl-P(H) phosphanyl substituted tert-butylacetylenes 7a,b (aryl: Mes or Mes?) undergo hydroboration with [HB(C6F5)2] to give the geminal vinylidene-bridged P/B Lewis pairs 8a,b. The treatment of 8a,b with benzonitrile, N-sulfinylaniline, and phenyl isothiocyanate, respectively, gives the addition products 12a,b, 13a,b, and 14 with proton transfer from the phosphorus to the more basic nitrogen site. The reaction of the FLPs 8a,b with carbon dioxide yields a doubly boron bonded addition product. The reaction of 8b with a conjugated ynone formally proceeded by trans-1,2-hydrophosphination of the alkyne at the geminal FLP framework to give the seven-membered heterocycle 21.
- Jian, Zhongbao,Kehr, Gerald,Daniliuc, Constantin G.,Wibbeling, Birgit,Erker, Gerhard
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supporting information
p. 11715 - 11721
(2017/09/18)
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- Synthetic strategies to bicyclic tetraphosphanes using P1, P2 and P4 building blocks
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Different reactions of Mes? substituted phosphanes (Mes? = 2,4,6-tri-tert-butylphenyl) led to the formation of the bicyclic tetraphosphane Mes?P4Mes? (5) and its unknown Lewis acid adduct 5·GaCl3. In this context, the endo-exo isomer
- Bresien, Jonas,Faust, Kirill,Hering-Junghans, Christian,Rothe, Julia,Schulz, Axel,Villinger, Alexander
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supporting information
p. 1998 - 2007
(2016/02/09)
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- Dimers and Trimers of Diphosphenes: A Wealth of Cyclo-Phosphanes
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Various new P-based ring systems were synthesised by transferring established reaction routes from NP chemistry to the analogous PP compounds. Due to the different electronic situations of phosphorus and nitrogen with respect to s and p character of the l
- Bresien, Jonas,Hering, Christian,Schulz, Axel,Villinger, Alexander
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supporting information
p. 12607 - 12615
(2016/08/25)
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- Phosphaalkenes in π-conjugation with acetylenic arenes
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(Chemical Equation Presented) Phosphaalkene Inclusion at the periphery of acetylenlc arenes results In decreased band gaps of the title compounds as verified by spectroscopic and electrochemical techniques. The electronic coupling between two 1-phosphahex
- Geng, Xue-Li,Hu, Qi,Schaefer, Bernhard,Ott, Sascha
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supporting information; experimental part
p. 692 - 695
(2010/04/02)
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- C,C-diacetylenic phosphaalkenes as heavy diethynylethene analogues
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(Chemical Equation Presented) Aseries of C,C-diacetylenic phosphaalkenes 1b-e has been prepared from 1-chloropenta-1,2-dien-4-ynes 6b-e in a reaction with Mes*PCl2 (Mes* = 2,4,6-(tBu) 3Ph) in the presence of LDA. Under ide
- Oeberg, Elisabet,Schaefer, Bernhard,Geng, Xue-Li,Pettersson, Jenny,Hu, Qi,Kritikos, Mikael,Rasmussen, Torben,Ott, Sascha
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experimental part
p. 9265 - 9273
(2010/03/03)
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- An unusual equilibrium chlorine atom transfer process and its potential for assessment of steric pressure by bulky aryls
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An unusually facile intermolecular chlorine atom transfer process has been discovered between the phospha-Wittig reagents ArPP 3 and ArPcl2(Ar is sterically hindered aryl group). The atom transfer process is catalyzed by added PMe 3.A mechanism is forwarded that is based upon a Me3P/Me3PCl2 couple that allows shuttling of chlorine atoms between ArP groups. This unique transfer process is exploited to evaluate the steric properties of aryl groups via an equilibrium process. Copyright
- Smith, Rhett C.,Shah, Shashin,Umezius, Eugenijus,Protasiewicz, John D.
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- Influence of ortho Methyl and Isopropyl Substituents on the Reactivity of N-t-Butyl P-Arylphosphonamidic Chlorides with Isopropylamine and t-Butylamine: Steric Acceleration of Metaphosphonimidate Formation by an Elimination-Addition Mechanism; Contrasting Behaviour of N,N-Dimethyl P-A...
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The two types of phosphonamidic chloride ArP(O)(Cl)NMe2, (5) and ArP(O)(Cl)NHBut (7) have been prepared with Ar=Ph, o-MeC6H4, 2,4,6-Me3C6H2, and 2,4,6-Pri3C6H2.Both types give the expected phosphonic diamide substitution products with PriNH2 and ButNH2 in MeCN, but the two types display contrasting reactivity.With ButNH2 the NMe2 substrates (5) become progressively less reactive as the degree of steric crowding increases, and although the decrease is quite small (70-fold overall) it seems consistent with an associative N2(P)> mechanism.These substrates react >=100 times faster with PriNH2, than with ButNH2 and in PriNH2-ButNH2 competitive experiments they give almost exclusively (>=99percent) the product derived from the less hindered PriNH2.For the NHBut substrates (7) with ButNH2, there is little difference in reactivity between the Ph and o-MeC6H4 compounds, and between the 2,4,6-Me3C6H2 and 2,4,6-Pri3C6H2 compounds, but remarkably the more crowded pair of substrates is the more reactive, by a factor of ca. 100.Also, in competitive experiments these substrates display relatively little preference for reaction with PriNH2.Here a dissociative elimination-addition mechanism, with a metaphosphonimidate intermediate, is seen to be important.A possible explanation of the steric acceleration is advanced.The ability of (7; Ar=Ph) to undergo substitution by elimination-addition makes possible the phosphonylation of unreactive nucleophiles such as ButOH and Pri2NH under mild conditions.
- Freeman, Sally,Harger, Martin J.
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p. 1399 - 1406
(2007/10/02)
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- REACTION OF A DIPHOSPHENE WITH VARIOUS HALOGENS
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Bis (2,4,6-tri-tert-butylphenyl)diphosphene reacts with various halogens to give the corresponding phosphonic dihalides, haloarene, and arene depending upon the halogen and solvent used.
- Yoshifuji, Masaaki,Shima, Ichiro,Shibayama, Katsuhiro,Inamoto, Naoki
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p. 411 - 414
(2007/10/02)
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- STABLE UNSYMMETRICAL DIPHOSPHENES
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Variation of the ortho-alkyl substituents in diaryldiphosphenes revealed that their stability is determined by steric hindrance.By suitable combinations of ortho-substituents, it was therefore possible to prepare the first relatively stable unsymmetrical
- Smit, C.N.,van der Knaap, Th.A.,Bickelhaupt, F.
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p. 2031 - 2034
(2007/10/02)
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