Monofluorinated indolizines 4, benzo[d]indolizines 7 and 4H-pyrrolo[1,2-a]benzimidazoles 8 were synthesized in moderate yields by 1,3-dipolar reaction between fluorinated vinyl tosylates 2a and N-ylides of pyridinium, isoquinolinium and benzimidazolinium, generated in situ from their halides salts. When the same N-ylides were allowed to react with 2,3,3-trifluoro-1-propenyl tosylate 2b, the unexpected product formylated indolizines and their derivatives 9 were obtained. The reaction mechanism is also proposed.

Several new 13-vertex closo-metallacarboranes of rare earths incorporating nido-and arachno-carborane ligands have been prepared and structurally characterized. They represent a new class of metallacarboranes bearing a h7-carboranyl ligand recently discovered in our laboratory. This work indicates that the substituents on carborane cage carbons may affect the overall molecular structures of the resultant 13-vertex closo-metallacarborane complexes, but have little influence on the interactions between the central metal ion and nido- or arachno-carborane ligand.

The intermolecular additions of alkyl halides to per-(or poly)fluorophenyl aromatic aldimines using zinc as a single-electron-transfer radical initiator have been studied in aqueous media. The reaction proceeds well for imines with different substituents at room temperature under air atmosphere and the corresponding fluorine-containing amines and 1,2-diamines are obtained in poor to good yields. A tentative reaction mechanism is proposed.

A versatile compound, Me2Si(C9H7)(C2B10H11) can be conveniently converted into the monoanion [Me2Si(C9H6)(C2B10H11)]Na, the dianion [Me2Si(C9H6)(C2B10H10)]Na2, and the trianion [Me2Si(C9H6)(C2B10H11)]K3 by treatment with 1 equiv or excess amounts of NaH or K metal in THF, respectively. Reaction of LnCl3 with 1 equiv of [Me2Si(C9H6)(C2B10H11)]Na in THF gave dichloride complexes [η5-Me2Si(C9H6)(C2B10H11)]LnCl2(THF)3 (Ln) Nd (1), Er (2)). They can further react with another equivalent of [Me2Si(C9H6)(C2B10H11)]Na to afford monochloride complexes [η5-Me2Si(C9H6)(C2B10H11)]2LnCl(THF)2 (Ln) Ce (3), Nd (4), Sm (5), Er (6)), which can also be prepared by treatment of LnCl3 with 2 equiv of [Me2Si(C9H6)-(C2B10H11)]Na in THF. 4 reacts with excess NaH in THF to produce [Na(THF)6][{η5:σ-Me2-Si(C9H6)(C2B10H10)}2Nd] (7), which can also be prepared from the reaction of NdCl3 with 2 equiv of [Me2Si(C9H6)(C2B10H10)]Na2 in THF. Treatment of 2 with 2 equiv of K metal at room temperature yielded [η5:η6-Me2Si(C9H6)(C2B10H11)]Er(THF)2 (8). Reaction of 6 with 1 equiv of NaH afforded [{η5:σ-Me2Si(C9H6)(C2B10H10)}{η5-Me2Si(C9H6)(C2B10H11)}]Er(μ-Cl)-Na(THF)3 (9), which can also be prepared from the reaction of 2 with 1 equiv of [Me2Si-(C9H6)(C2B10H10)]Na2 in THF. Treatment of 9 with a mixture of 1 equiv of NaOH and excess NaH in THF generated the dinuclear complex [Na2(THF)11][{η5:σ-Me2Si(C9H6)(C2B10H10)}-{μ-η5:σ-(C9H6)SiMe2O}Er]2 (10). Treatment of Me2Si(C9H7)(C2B10H11) with excess NaH in THF under UV-light followed by reaction with 1 equiv of LnCl3 resulted in the isolation of unprecedented biscarborane compounds [LnCl2(THF)5][μ-CH-(closo-C2B10H11)-nido-CB10H11] (Ln) Er (11), Y (12)). All of these complexes were characterized by various spectroscopic and elemental analyses. The solid-state structures of 7 and 9-12 were confirmed by singlecrystal X-ray analyses.

Reaction of Me2Si(C9H7)Cl with 1 equiv of Li2C2B10H10 gave, after hydrolysis, the new versatile ligand Me2Si(C9H7)(C2B10H11) (1). 1 can be conveniently converted into the monoanion [Me2Si(C9H6)(C2B10H11)]-(2) and the dianion [Me2Si(C9H6)(C2B10H10)]2-(3) by treatment with 1 equiv or excess amounts of NaH, respectively. Treatment of SmI2 with 2 in THF gave the unexpected redox product [η5:η6-Me2Si(C9H6)(C2B10H11)]Sm(THF)2 (4). Reaction of SmI2 with 1 equiv of 3 in THF, followed by reaction with 2, gave the unexpected C-H bond reduction product [{η5:σ-Me2Si(C9H6)(C2B10H10)}2Sm][Na(THF)6] (5). In contrast, reaction of YbI2 with 1 or 2 equiv of 2 afforded [{η5-Me2Si(C9H6)(C2B10H11)}Yb(σ-I)(THF)2]2 (6) or [η5-Me2Si(C9H6)(C2B10H11)]2Yb(THF)2 (7), respectively. Treatment of YbI2 with 1 equiv of 3 in THF gave [η5:σ-Me2Si(C9H6)(C2B10H10)]Yb(THF)3 (8), which is the first mixed-ligand organolanthanide(II) complex containing both Ln-C ð and ó bonds to be reported. 8 can also be prepared from the reaction of 6 with excess NaH in THF. Reaction of 8 with 1 equiv of 2 in THF yielded [η5-Me2Si(C9H6)(C2B10H11)]Yb(THF)[(μ-η5):σ-Me2Si(C9H6)(C2B10H10)]Na-(THF)3 (9), which can also be prepared by reaction of 7 with 1 equiv of NaH in THF. These new complexes have been fully characterized by 1H, 13C, and 11B NMR, IR spectroscopy, and elemental analyses. The molecular structures of 4, 5, 8, and 9 have been further confirmed by single-crystal X-ray analyses.