17873-10-8Relevant academic research and scientific papers
Heterobimetallic s-block hydrides by σ-bond metathesis
Liptrot, David J.,Hill, Michael S.,Mahon, Mary F.
, p. 9871 - 9874 (2014)
Reactions between PhSiH3 and alkali-metal diamidoalkylmagnesiates ([M{N(SiMe3)2}2MgBu], M=Li, Na, K) provide either selective alkyl metathesis or the formation of polyhydride aggregates contingent upon the identity of the Group 1 metal. In the case of [M{N(SiMe3)2}2MgBu], this reactivity results in a structurally unprecedented dodecametallic decahydride cluster species.
Ring-Shaped Phosphinoamido-Magnesium-Hydride Complexes: Syntheses, Structures, Reactivity, and Catalysis
Fohlmeister, Lea,Stasch, Andreas
, p. 10235 - 10246 (2016/07/19)
A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L?=Ph2PNDip?, Dip=2,6-diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand ge
Iron-copper cooperative catalysis in the reactions of alkyl grignard reagents: Exchange reaction with alkenes and carbometalation of alkynes
Shirakawa, Eiji,Ikeda, Daiji,Masui, Seiji,Yoshida, Masatoshi,Hayashi, Tamio
supporting information; experimental part, p. 272 - 279 (2012/03/07)
Iron-copper cooperative catalysis is shown to be effective for an alkene-Grignard exchange reaction and alkylmagnesiation of alkynes. The Grignard exchange between terminal alkenes (RCH=CH2) and cyclopentylmagnesium bromide was catalyzed by FeCl3 (2.5 mol %) and CuBr (5 mol %) in combination with PBu3 (10 mol %) to give RCH2CH 2MgBr in high yields. 1-Alkyl Grignard reagents add to alkynes in the presence of a catalyst system consisting of Fe(acac)3, CuBr, PBu3, and N,N,N″,N″-tetramethylethylenediamine to give β-alkylvinyl Grignard reagents. The exchange reaction and carbometalation take place on iron, whereas copper assists with the exchange of organic groups between organoiron and organomagnesium species through transmetalation with these species. Sequential reactions consisting of the alkene-Grignard exchange and the alkylmagnesiation of alkynes were successfully conducted by adding an alkyne to a mixture of the first reaction. Isomerization of Grignard reagents from 2-alkyl to 1-alkyl catalyzed by Fe-Cu also is applicable as the first 1-alkyl Grignard formation step.
β-Diketiminate-Stabilized Magnesium(I) Dimers and Magnesium(II) Hydride Complexes: Synthesis, Characterization, Adduct Formation, and Reactivity Studies
Bonyhady, Simon J.,Jones, Cameron,Nembenna, Sharanappa,Stasch, Andreas,Edwards, Alison J.,McIntyre, Garry J.
experimental part, p. 938 - 955 (2010/08/20)
The preparation and characterization of a series of magnesium(II) iodide complexes incorporating β-diketiminate ligands of varying steric bulk and denticity, namely, [(ArNC-Me)2CH]- (Ar = phenyl, (PhNacnac), mesityl (MesNacnac), or 2,6-diisopropyl-phenyl (Dipp, DippNacnac)), [(DippNC-tBu) 2CH]- (tBuNacnac), and [(DippNC-Me)(Me2NCH 2CH2NCMe)CH]- (DmedaNacnac) are reported. The complexes [(PhNacnac)MgI(OEt2)], [(MesNacnac)MgI(OEt2)], [(DmedaNacnac)MgI(OEt2)], [(MesNacnac)MgI-(thf)], [(DippNacnac)MgI(thf)], [(tBuNac-nac)MgI], and [(tBuNacnac)MgI-(DMAP)] (DMAP = 4-dimethylamino-pyridine) were shown to be monomeric by X-ray crystallography. In addition, the related β-diketiminato beryllium and calcium iodide complexes, [(MesNacnac)BeI] and [{(DippNacnac)-CaI(OEt2)} 2] were prepared and crystallographically characterized. The reductions of all metal(II) iodide complexes by using various reagents were attempted. In two cases these reactions led to the magnesium(I) dimers, [(MesNacnac)MgMg(MesNacnac)] and [(tBuNacnac)MgMg(tBuNacnac)]. The reduction of a 1:1 mixture of [(DippNacnac)MgI(OEt2)] and [(MesNacnac)MgI(OEt 2)] with potassium gave a low yield of the crystallo-graphically characterized complex [(DippNacnac)Mg(μ-H)(μ-I)Mg(MesNacnac)]. All attempts to form beryllium(I) or calcium(I) dimers by reductions of [(MesNacnac)BeI], [{(DippNacnac)CaI(OEt2)}2], or [{(tBuNacnac)CaI(thf)}2] have so far been unsuccessful. The further reactivity of the magnesium(I) complexes [(MesNacnac)MgMg(MesNacnac)] and [(tBuNacnac)MgMg(tBuNacnac)] towards a variety of Lewis bases and unsaturated organic substrates was explored. These studies led to the complexes[(MesNacnac) Mg(L)Mg(L)(MesNacnac)](L = THF or DMAP), [(MesNacnac)Mg-(μ-AdN 6Ad)Mg(MesNacnac)] (Ad = 1- adamantyl), [(tBuNacnac)Mg(μ-Ad-N 6Ad)Mg(tBuNacnac)], and [(MesNacnac)Mg(μ-tBu2N 2C2O2)Mg- (MesNacnac)] and revealed that, in general, the reactivity of the magnesium(I) dimers is inversely proportional to their steric bulk. The preparation and characterization of [(tBuNacnac)Mg(μ- H)2Mg(tBuNacnac)] has shown the compound to have different structural and physical properties to [(tBuNacnac)-MgMg(tBuNacnac)]. Treatment of the former with DMAP has given [(tBuNacnac)Mg(H)(DMAP)], the X-ray crystal structure of which disclosed it to be the first structurally authenticated terminal magnesium hydride complex. Although attempts to prepare [(MesNacnac)Mg(μ-H) 2Mg(MesNacnac)] were not successful, a neutron diffraction study of the corresponding magnesium(I) complex, [(MesNacnac)Mg-Mg(MesNacnac)] confirmed that the compound is devoid of hydride ligands.
