6163-58-2Relevant articles and documents
A family of rhodium and iridium complexes with semirigid benzylsilyl phosphines: From bidentate to tetradentate coordination modes
Corona-González, María Vicky,Zamora-Moreno, Julio,Cuevas-Chávez, Cynthia A.,Rufino-Felipe, Ernesto,Mothes-Martin, Emmanuelle,Coppel, Yannick,Mu?oz-Hernández, Miguel A.,Vendier, Laure,Flores-Alamo, Marcos,Grellier, Mary,Sabo-Etienne, Sylviane,Montiel-Palma, Virginia
, p. 8827 - 8838 (2017)
The synthesis of a new trisbenzylsilanephosphine P{(o-C6H4CH2)SiMe2H}3 (1) is shown to proceed with high yields from P(o-tolyl)3. Compound 1 coordinates to the Rh and Ir dimers [MCl(COD)]2 (M = Rh, Ir) in a tetradentate or tridentate fashion, depending on the strict exclusion of water. The dimeric compounds [ClM(SiMe2CH2-o-C6H4)2P(o-C6H4-CH2SiMe2H)]2, 2Rh and 2Ir, feature a tetradentate coordination of the starting ligand with P and two Si atoms as well as a non-classical agostic Si-H group. The presence of adventitious water in the solvents leads to the formation of two new complexes [(μ2-Cl)2M2(SiMe2CH2-o-C6H4)2P(o-C6H4-CH2SiMe2OSiMe2CH2-o-C6H4-)P(SiMe2CH2-o-C6H4)2], 3Rh and 3Ir, which feature a siloxane bridge through Si-H bond breaking in 2. Reaction of [RhCl(COD)]2 with the bisbenzylsilanephosphine PhP{(o-C6H4CH2)SiMe2H}2 leads to the formation of compound 4Rh which features also a dimeric structure with the SiPSi ligand coordinated through the two silicon atoms, one of which occupies the apical position of a square-pyramidal geometry in the solid state, while the second is disposed equatorially trans to π-donor Cl. Finally, bidentate coordination of a PSi ligand is achieved by reaction of [RhCl(COD)]2 with Ph2P{(o-C6H4CH2)SiMe2H} which leads to the monometallic species [RhCl(SiMe2CH2-o-C6H4-PPh2)2], 5Rh, incorporating two chelating PSi ligands and maintaining a Cl ligand.
Hadjikakou, S. K.,Aslanidis, P.,Karagiannidis, P.,Aubry, A.,Skoulika, S.
, p. 129 - 136 (1992)
A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
Taylor, Nicholas P.,Gonzalez, Jorge A.,Nichol, Gary S.,García-Domínguez, Andrés,Leach, Andrew G.,Lloyd-Jones, Guy C.
supporting information, p. 721 - 729 (2022/01/04)
The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
The Trityl-Cation Mediated Phosphine Oxides Reduction
Landais, Yannick,Laye, Claire,Lusseau, Jonathan,Robert, Frédéric
supporting information, p. 3035 - 3043 (2021/05/10)
Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).
