14090-06-3Relevant academic research and scientific papers
Complexation and Versatile Reactivity of a Highly Lewis Acidic Cationic Mg Complex with Alkynes and Phosphines
Pahl, Jürgen,Stennett, Tom E.,Volland, Michel,Guldi, Dirk M.,Harder, Sjoerd
, p. 2025 - 2034 (2019)
[(BDI)Mg+][B(C6F5)4?] (1; BDI=CH[C(CH3)NDipp]2; Dipp=2,6-diisopropylphenyl) was prepared by reaction of (BDI)MgnPr with [Ph3C+][B(C6F5)4?]. Addition of 3-hexyne gave [(BDI)Mg+?(EtC≡CEt)][B(C6F5)4?]. Single-crystal X-ray analysis, NMR investigations, Raman spectra, and DFT calculations indicate a significant Mg-alkyne interaction. Addition of the terminal alkynes PhC≡CH or Me3SiC≡CH led to alkyne deprotonation by the BDI ligand to give [(BDI-H)Mg+(C≡CPh)]2?2 [B(C6F5)4?] (2, 70 %) and [(BDI-H)Mg+(C≡CSiMe3)]2?2 [B(C6F5)4?] (3, 63 %). Addition of internal alkynes PhC≡CPh or PhC≡CMe led to [4+2] cycloadditions with the BDI ligand to give {Mg+C(Ph)=C(Ph)C[C(Me)=NDipp]2}2? 2 [B(C6F5)4?] (4, 53 %) and {Mg+C(Ph)=C(Me)C[C(Me)=NDipp]2}2?2 [B(C6F5)4?] (5, 73 %), in which the Mg center is N,N,C-chelated. The (BDI)Mg+ cation can be viewed as an intramolecular frustrated Lewis pair (FLP) with a Lewis acidic site (Mg) and a Lewis (or Br?nsted) basic site (BDI). Reaction of [(BDI)Mg+][B(C6F5)4?] (1) with a range of phosphines varying in bulk and donor strength generated [(BDI)Mg+?PPh3][B(C6F5)4?] (6), [(BDI)Mg+?PCy3][B(C6F5)4?] (7), and [(BDI)Mg+? PtBu3][B(C6F5)4?] (8). The bulkier phosphine PMes3 (Mes=mesityl) did not show any interaction. Combinations of [(BDI)Mg+][B(C6F5)4?] and phosphines did not result in addition to the triple bond in 3-hexyne, but during the screening process it was discovered that the cationic magnesium complex catalyzes the hydrophosphination of PhC≡CH with HPPh2, for which an FLP-type mechanism is tentatively proposed.
Alkyl scandium complexes coordinated by dianionic O,N,N- and O,N,O-ligands derived from Schiff bases
Cherkasov, Anton V.,Gurina, Galina A.,Kissel, Alexander A.,Ob'edkov, Anatoly M.,Trifonov, Alexander A.
, p. 631 - 634 (2021/11/26)
The reactions of imino phenols 3,5-But2-2-HOC6H2CH=NX (X = 8-C9H6N, 2-MeO-5-MeC6H3 and 2-PhOC6H4) with Sc(CH2SiMe3)3/
A bench-stable copper photocatalyst for the rapid hydrophosphination of activated and unactivated alkenes
Dannenberg, Steven G.,Waterman, Rory
supporting information, p. 14219 - 14222 (2020/11/24)
Cu(acac)2 (1) is a highly active catalyst for the hydrophosphination of alkenes. Photocatalytic conditions are critical, and provide high conversions with unactivated substrates that have never before been reported with an air-stable catalyst or at ambient temperature. The commercial availability, ease of use, and broad substrate scope of compound 1 make hydrophosphination more available to synthetic chemists.
Lithium-Aluminate-Catalyzed Hydrophosphination Applications
Pollard, Victoria A.,Young, Allan,McLellan, Ross,Kennedy, Alan R.,Tuttle, Tell,Mulvey, Robert E.
supporting information, p. 12291 - 12296 (2019/08/02)
Synthesized, isolated, and characterized by X-ray crystallography and NMR spectroscopic studies, lithium phosphidoaluminate iBu3AlPPh2Li(THF)3 has been tested as a catalyst for hydrophosphination of alkynes, alkenes, and carbodiimides. Based on the collective evidence of stoichiometric reactions, NMR monitoring studies, kinetic analysis, and DFT calculations, a mechanism involving deprotonation, alkyne insertion, and protonolysis is proposed for the [iBu3AlHLi]2 aluminate catalyzed hydrophosphination of alkynes with diphenylphosphine. This study enhances further the development of transition-metal-free, atom-economical homogeneous catalysis using common sustainable main-group metals.
N-Heterocyclic Carbene Non-Innocence in the Catalytic Hydrophosphination of Alkynes
Blackaby, William J. M.,Neale, Samuel E.,Isaac, Connie J.,Sabater, Sara,Macgregor, Stuart A.,Whittlesey, Michael K.
, p. 1893 - 1897 (2019/04/14)
Studies on alkyne hydrophosphination employing nickel-NHC catalysts (NHC=N-heterocyclic carbene) revealed that the free N-alkyl substituted NHCs themselves were catalytically active. DFT calculations showed the mechanism involves the NHC acting as a Br?ns
Photocatalytic Hydrophosphination of Alkenes and Alkynes Using Diphenylphosphine and Triamidoamine-Supported Zirconium
Novas, Bryan T.,Bange, Christine A.,Waterman, Rory
supporting information, p. 1640 - 1643 (2019/01/04)
Reactions of alkene or alkyne with diphenylphosphine and catalytic [κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr (1) are greatly enhanced under photolysis, providing viable catalytic hydrophosphination with a broad substrate scope. Whereas diphenylphosphine had been an inaccessible substrate under thermal conditions, complete conversion of alkene substrates to tertiary phosphine is achieved in as little as four hours at ambient temperature with 1 under ultraviolet irradiation. Previously inactive alkenes are now hydrophosphination substrates with diphenylphosphine to produce tertiary phosphine ligands possessing tunable steric and electronic properties.
Thermally Stable Ln(II) and Ca(II) Bis(benzhydryl) Complexes: Excellent Precatalysts for Intermolecular Hydrophosphination of C-C Multiple Bonds
Selikhov, Alexander N.,Plankin, Gleb S.,Cherkasov, Anton V.,Shavyrin, Andrey S.,Louyriac, Elisa,Maron, Laurent,Trifonov, Alexander A.
, p. 5325 - 5334 (2019/04/17)
A series of Ln(II) and Ca(II) bis(alkyl) complexes with bulky benzhydryl ligands, [(p-tBu-C6H4)2CH]2M(Ln) (M = Sm, L = DME, n = 2 (1); M = Sm, Yb, Ca, L = TMEDA, n = 1 (2, 3, 4), were synthesized by t
Reductive Elimination at Carbon under Steric Control
Tolentino, Daniel R.,Neale, Samuel E.,Isaac, Connie J.,MacGregor, Stuart A.,Whittlesey, Michael K.,Jazzar, Rodolphe,Bertrand, Guy
supporting information, p. 9823 - 9826 (2019/07/04)
It has been previously demonstrated that stable singlet electrophilic carbenes can behave as metal surrogates in the activation of strong E-H bonds (E = H, B, N, Si, P), but it was believed that these activations only proceed through an irreversible activation barrier. Herein we show that, as is the case with transition metals, the steric environment can be used to promote reductive elimination at carbon centers.
Calcium Amido Complexes Coordinated by Tridentate Amidinate Ligands: Synthesis, Structures and Catalytic Activity in Olefin Hydrophosphination and Polymerization of Cyclic Esters
Tolpygin, Aleksei O.,Cherkasov, Anton V.,Fukin, Georgy K.,Kovylina, Tatyana A.,Lyssenko, Konstantin A.,Trifonov, Alexander A.
, p. 4289 - 4296 (2019/08/15)
The reactions of [(Me3Si)2N]2Ca(thf)2 with amidines 2-(Ph2P=NPh)C6H4NHC(tBu)=N(2,6-R2C6H3) {R = iPr (L1H); R = Me (L2H)} af
Regioselective Single and Double Hydrophosphination and Hydrophosphinylation of Unactivated Alkynes
Basiouny, Miriam M. I.,Dollard, Deborah A.,Schmidt, Joseph A. R.
, p. 7143 - 7153 (2019/08/26)
A lanthanum-based N,N-dimethylbenzylamine complex was used as a precatalyst for both hydrophosphination and hydrophosphinylation of alkynes under mild conditions. In the case of hydrophosphination, the catalyst induced monoaddition with high regiospecific
