John W. Gilje

Lanthanide alkoxides. III: Four-coordinate anionic neodymium(III) alkoxides and amides

Abstract Tetracoordinate anionic neodymium(III) alkoxides and amides are obtained by adduct formation of Nd[OC(tBu)3]3 (1) and Nd[N(SiMe3)2]3 (2) with either LiCl or LiOSiMe3. The compounds (THF)3Li(μ-Cl)Nd[OC(tBu)3]3 (3), (THF)3Li(μ-Cl)Nd [N(SiMe3)2]3 (4) and [Li(THF)4][(Me3Si)2N3Nd(OSiMe3)] (5) have been characterized by single-crystal X-ray analyses.

Struktur und reaktivität von ytterbiumbenzamidinaten

Abstract The ytterbium(II) benzamidinates [RC6H4C(NSiMe3)2]2Yb(THF)2 (1a: R  H, 1b: R  OMe) react with diaryl diselenides and ditellurides to give ytterbium(III) complexes of the type [RC6H4C(NSiMe3)2]2Yb(SeR′)(THF) (2: R  H, R′  Ph; 3: R  H, R′  Mes) and [RC6H4C-(NSiMe3)2]2Yb(TeR′)(THF) (4: R  OMe, R′  Mes), respectively. The molecular structure of [PhC(NSiMe3)2]2Yb(SeMes)(THF) (3) has been determined by X-ray crystallography (triclinic, space group P 1 , a 1064.9(3), b 1377.1(3), c 3690(3) pm, α 68.61(2), β 89.46(3), γ 72.82(1)°, Z = 4, 10531 observed reflexions, R = 0.045). Moreover the strongly temperature-dependent 1H NMR spectra of 2 and 3 are discussed and 171Yb NMR spectra of some ytterbium(II) chelate complexes are reported.

The crystal and molecular structure of pentamethylcyclopentadienyl Grignard reagent: [Cp*Mg(thf)μ-Cl]2

Abstract The crystal and molecular structure of pentamethylcyclopentadienyl Grignard reagent has been determined by X-ray diffraction in the monoclinic space group C 2/ c ; cell parameters a 21.51(2) A, b 11.778(6) A, c 14.04(1) A, α 90°, γ 90°, β 95.17(7)°, V 3543(5) A 3 , Z = 4 dimers, with R = 0.1047, R w = 0.0938, R G = 0.1068. The pentamethylcyclopentadienyl Grignard reagent is a dimer in which chloro ligands bridge two Mg 2+ ions which are each coordinated to a η 5 -Cp * group and a THF molecule. A disordered toluene molecule is also found in the crystal lattice.

Actinidkomplexe mit Tripodliganden: Synthese und Struktur von [CpCo{P(O)(OEt)2}3]UCl3(THF)

The reaction of UCl4 with Na[CpCo{P(O)(OEt)2}3] (1) in THF yields the monosubstituted derivative [CpCo{P(O)(OEt)2}3]UCl3(THF) (2). The coordinated THF molecule in 2 is easily removed under vacuum to give [CpCo{P(O)(OEt)2}3]UCl3 (3). ThCl4 reacts with 1 to give the disubstituted product [CpCo{P(O)(OEt)2}3]2ThCl2 (4). A mixed-ligand cyclopentadienyl uranium complex, [CpCo{P(O)(OEt)2}3]CpUCl2 (5) is obtained by treatment of CpUCl3(THF)2 with 1.

Lanthanide alkoxides—II. Heterobimetallic alkoxides containing divalent lanthanides

Abstract Treatment of LnI 2 with K[Al(OPr i ) 4 ] in THF solution (molar ratio 1: 2) yields the air-sensitive heterobimetallic alkoxides Ln II [Al 3 (OPr i ) 11 ] [Ln = Sm ( 1 ), Yb ( 2 )].

Relationship between the photoelectron spectra and torsional barriers of aminophosphines

The trends in the nitrogen and phosphorus lone-pair ionization potentials of Me2NP(CF3)2(1), Me2NP(Cl)CF3, (2), and Me2NPCl2(3) suggest that the P–N torsional barriers in aminophosphines arise predominantly from steric and lone pair–lone pair repulsion effects.

Rearrangements in fluxional trifluorophosphoranes: 1H nuclear magnetic resonance study

Dynamical 1H n.m.r. studies of the fluxional trifluorophosphoranes, H2PF3(1) and CF3(H)Pf3(2) are reported and the observations are discussed in terms of rearrangement modes.