122279-48-5Relevant academic research and scientific papers
A hydroboration route to geminal P/B frustrated Lewis pairs with a bulky secondary phosphane component and their reaction with carbon dioxide
Jian, Zhongbao,Kehr, Gerald,Daniliuc, Constantin G.,Wibbeling, Birgit,Erker, Gerhard
, p. 11715 - 11721 (2017)
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.
New Reactivity Patterns in 3H-Phosphaallene Chemistry [Aryl-P=C=C(H)-tBu]: Hydroboration of the C=C Bond, Deprotonation and Trimerisation
Tendyck, Jonas C.,Hepp, Alexander,Würthwein, Ernst-Ulrich,Uhl, Werner
, p. 15977 - 15988 (2020)
3H-Phosphaallenes, R?P=C=C(H)C?R’ (3), are accessible in a multigram scale on a new and facile route and show a fascinating chemical reactivity. BH3(SMe2) and 3 a (R=Mes*, R’=tBu) afforded by hydroboration of the C=C bonds of two phosphaallene molecules an unprecedented borane (7) with the B atom bound to two P=C double bonds. This compound represents a new FLP based on a B and two P atoms. The increased Lewis acidity of the B atom led to a different reaction course upon treatment of 3 a with H2B-C6F5(SMe2). Hydroboration of a C=C bond of a first phosphaallene is followed in a typical FLP reaction by the coordination of a second phosphaallene molecule via B?C and P?B bond formation to yield a BP2C2 heterocycle (8). Its B?P bond is short and the B-bound P atom has a planar surrounding. Treatment of 3 a with tBuLi resulted in deprotonation of the β-C atom of the phosphaallene (9). The Li atom is bound to the P atom as demonstrated by crystal structure determination, quantum chemical calculations and reactions with HCl, Cl-SiMe3 or Cl-PtBu2. The thermally unstable phosphaallene Ph?P=C=C(H)-tBu gave a unique trimeric secondary product by P?P, P?C and C?C bond formation. It contains a P2C4 heterocycle and was isolated as a W(CO)4 complex with two P atoms coordinated to W (15).
3H-Phosphaallenes Revisited: Facile Synthesis by Hydroalumination of Alkynylphosphines and β-Elimination, Stability and Trapping of Transient Species by Coordination to Transition Metal Atoms
Kl?cker, Hans,Tendyck, Jonas C.,Keweloh, Lukas,Hepp, Alexander,Uhl, Werner
, p. 4793 - 4807 (2019/03/13)
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
Coupling of Alkynyl(2,4,6-tri-tert-butylphenyl)phosphanes with Cuprous Chloride
Maerkl, Gottfried,Henning, Ruediger
, p. 2059 - 2064 (2007/10/03)
Coupling of alkynyl(2,4,6-tri-tert-butylphenyl)phosphanes 2 with n-butyllithium and cuprous chloride gives 3,4-diphospha-1,5-hexadiynes 3 or cuprous chloride complexes 8 of 3,4-bis(phosphinidene)cyclobutenes 5, depending on the bulkiness of the substituen
3H-PHOSPHAALLEN-ALKINYL-1H-PHOSPHAN-TAUTOMERE
Maerkl, G.,Reitinger, S.
, p. 463 - 466 (2007/10/02)
The title compounds are prepared for the first time by reaction of 2,4,6-tris(tert-butyl)phenylchlorophosphane with Li-resp.Mg-acetylides
