106316-57-8Relevant articles and documents
Lanthanoid Pseudo-Grignard Reagents: A Major Untapped Resource
Ali, Safaa H.,Deacon, Glen B.,Junk, Peter C.,Hamidi, Shima,Wiecko, Michal,Wang, Jun
, p. 230 - 242 (2018)
Pseudo-Grignard reagents PhLnI (Ln=Yb, Eu), readily prepared by the oxidative addition of iodobenzene to ytterbium or europium metal at ?78 °C in tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME), react with a range of bulky N,N′-bis(aryl)formamidines to generate an extensive series of LnII or more rarely LnIII complexes, namely [Eu(DippForm)I(thf)4]?thf (1), [{EuI2(dme)2}2] (2), [Eu(XylForm)I(dme)2]?0.5 dme (3 a), [Eu(XylForm)I(dme)(μ-dme)]n (3 b), [{Eu(XylForm)I(μ-OH)(thf)2}2] (4), [Yb(DippForm)I(thf)3]?thf (5 a), [Yb(DippForm)I2(thf)3]?2 thf (5 b), [{Yb(MesForm)I(thf)2}2] (6), [{Yb(XylForm)I(thf)2}2] (7 a), and [Yb(XylForm)2I(dme)]?dme (7 b) {(Form=ArNCHNAr; XylForm (Ar=2,6-Me2C6H3), MesForm (Ar=2,4,6-Me3C6H2), DippForm (Ar=2,6-iPr2C6H3)}. Reaction of PhEuI and MesFormH in DME consistently gave 2, and reaction with XylFormH in THF gave 4. Europium complexes 1 and 3 a are seven-coordinate divalent monomers, whilst 3 b is a seven-coordinate dme-bridged polymer. Complex 5 a of the smaller YbII is a six-coordinate monomer, but the related 6 and 7 a are six-coordinate iodide-bridged dimers. 4 is a trivalent seven-coordinate hydroxide-bridged dimer, whereas complexes 5 b and 7 b are seven-coordinate monomeric YbIII derivatives. A characteristic structural feature is that iodide ligands are cisoid to the formamidinate ligand. To illustrate the synthetic scope of the pseudo-Grignard reagents, [Yb(Ph2pz)I(thf)4] (Ph2pz=3,5-diphenylpyrazolate) was oxidised with 1,2-diiodoethane to afford seven-coordinate monomeric pyrazolato-ytterbium(III) iodide [Yb(Ph2Pz)I2(thf)3] (8) in high yield, whilst metathesis between [Yb(Ph2pz)I(thf)4] and NaCp (Cp=C5H5) gave [Yb(C5H5)(Ph2pz)(thf)]n (9), a nine-coordinate η5:η5-Cp-bridged coordination polymer. Reaction of the pseudo-Grignard reagent MeYbI with KN(SiMe3)2 gave [K(dme)4][Yb{N(SiMe3)2}3] (10) with a charge-separated three-coordinate homoleptic [Yb{N(SiMe3)2}3]? anion, a complex that could be obtained in high yield by deliberate synthesis from YbI2 and KN(SiMe3)2 in DME.
Organolanthanoid-halide synthons - A new general route to monofunctionalized lanthanoid(ii) compounds?
Wiecko, Michal,Deacon, Glen B.,Junk, Peter C.
, p. 5076 - 5078 (2010/10/02)
New EuII and YbII complexes [Ln(Ph 2pz)I(thf)4] were synthesized from the corresponding metals and 3,5-diphenylpyrazole (HPh2pz) using iodobenzene as oxidizing agent. In the absence of the pyrazole, the charge separated Yb II/YbIII complex [{Yb(dme)4}{YbPh 4(dme)}2] has been isolated. The Royal Society of Chemistry 2010.
The reaction of ytterbium with N-iodo-triphenylphosphaneimine. Crystal structures of Yb2I(THF)2(NPPh3) · 2 THF, [YbI2(HNPPh3)(DME)2], and [{YbI2(DME)2}2(μ-DME)]
Groeb, Thorsten,Seybert, Gerd,Massa, Werner,Dehnicke, Kurt
, p. 349 - 353 (2008/10/08)
When treated with ultrasound, the reaction of ytterbium powder with INPPh3 in tetrahydrofuran leads to [YbI2(THF)4] and to the mixed-valence phosphoraneiminato complex [Yb2I(THF)2(NPPh3)4] · 2 THF (1), which forms red single-crystals. In the analogous reaction in 1,2-dimethoxyethane (DME) only the ytterbium(II) iodide solvates [YbI2(HNPPh3)(DME)2] (2) and [{YbI2(DME)2}2 · (μ-DME)] (3) can be isolated, which form yellow single crystals. All compounds were characterized by crystal structure analyses. 1: Space group P1, Z = 2, lattice dimensions at -80 °C: a = 1337.6(5), b = 1389.6(5), c = 2244.2(17) pm; α = 86.11(7)°, β = 88.06(7)°, γ = 88.63(4)°; R = 0.0759. In 1 the two ytterbium atoms are connected via the N atoms of two phosphoraneiminato groups (NPPh3-) to form a planar Yb2N2 fourmembered ring. The structure can also be described as an ion pair consisting of [YbI(THF)2]+ and [Yb(NPPh3)4]-· 2: Space group P21 Z = 2, lattice dimensions at -80 °C: a = 811.9(1), b = 1114.0(1), c = 1741.3(1) pm; β = 95.458(5)°; R = 0.0246. 2 forms molecules in which the ytterbium atom is coordinated in a pentagonal-bipyramidal fashion with the iodine atoms in the axial positions. The O atoms of the two DME-chelates and the N atom of the phosphaneimine ligand HNPPh3 are in the equatorial positions. 3: Space group P1, Z = 2, lattice dimensions at -70 °C: a = 817.5(1), b = 1047.7(1), c = 1115.5(2) pm; α = 90.179(10)°, β = 97.543(15)°, γ = 91.087(12)°; R = 0.0317. 3 has a dimeric molecular structure, in which the two fragments {YbI2(DME)2} are connected centrosymmetrically via a μ-DME bridge. As in 2, the ytterbium atoms are coordinated in a pentagonal-bipyramidal fashion with the iodine atoms in the axial positions, as well as with the two DME chelates and with one O atom each of the μ-DME ligand in the equatorial positions.
