Lewis superacid with higher fluoride ion affinity than SbF5.

Substituted 4-/7-halo-1H-indenes and 5-methyl-3-bromo-4-/6H-cyclopenta[b]thiophenes were shown to be convenient starting materials for Suzuki−Miyaura, Negishi, and Murahashi protocols to give the corresponding aryl-subsituted indenes and cyclopenta[b]thiophenes of importance for further synthesis of ansa-metallocenes. Alternatively, (2-methyl-1H-inden-4-yl)boronic acid and (1-methoxy-2-methyl-2,3-dihydro-1H-inden-4-yl)boronic acid as well as the respective organozinc and -magnesium reagents can be used for synthesizing aryl-subsituted indenes via the Pd-catalyzed reactions with aryl halides. These synthetic methods were shown to have a very broad scope to afford libraries of aryl-substituted indenes. Finally, synthesis and structure characterization of several representative chiral ansa-zirconocenes, potentially useful as components of highly active and stereoselective olefin polymerization catalysts, have been performed.

A series of novel, low‐valent germanium compounds 2a–2j based on four diethylenetriamines 1a–1d, (methyl)bis(pyrrol‐2‐ylmethyl)amine (1e), N,N′‐(sulfanediyldibenzene‐2,1‐diyl)bis(pentafluoroaniline) (1f), N,N′‐(oxydibenzene‐2,1‐diyl)bis(pentafluoroaniline) (1g), and (pentafluorophenyl)amines 1i and 1j have been obtained either by the reaction of Ge[N(SiMe3)2]2 with various diamines (1a–1e) or by the metathesis reaction of [GeCl2·dioxane] with lithium amides. The oxidative insertion (with halogenation reagents, MeI, disulfides), [1+4] cycloaddition, and oxidation reactions of the synthesized germylenes were investigated. The compositions and structures of the novel compounds were established by elemental analysis, 1H and 13C NMR spectroscopy, and X‐ray diffraction analysis (germylenes 2b, 2i, 2j, Ge4+ compounds 5b, 7a, 7b, 8, 10, 11). All the synthesized germylenes are monomeric.

Syntheses of a series of the title compounds, viz., N(CH2CH2NR)3M−X (1, M = Si, X = Me, R = SiMe3; 2, M = Si, X = Et, R = SiMe3; 3, M = Si, X = n-Bu, R = SiMe3; 4, M = Si, X = vinyl, R = SiMe3; 5, M = Si, X = Ph, R = SiMe3; 6, M = Ge, X = Me, R = SiMe3; 7, M = Ge, X = n-Bu, R = SiMe3; 8, M = Ge, X = Ph, R = SiMe3; 9, M = Sn, X = n-Bu, R = SiMe3; 10, M = Sn, X = Ph, R = SiMe3; 11, M = Si, X = vinyl, R = Me; 12, M = Ge, X = Me, R = Me) by the reaction of X−MCl3 with N(CH2CH2NSiMe3Li)3 or with N(CH2CH2NMeLi)3 are reported. Reactions of the novel compounds X−Ge(NMe2)3 (15, X = Ph; 16, X = 1-naphthyl; 17, X = 9-antracenyl; 18, X = 9-phenantrenyl) with N(CH2CH2NHMe)3 or N(CH2CH2NH2)3 resulted in new 1-arylazagermatranes, N(CH2CH2NMe)3Ge−X (19, X = Ph; 20, X = 1-naphthyl; 21, X = 9-antracenyl; 22, X = 9-phenantrenyl) and N(CH2CH2NH)3Ge−X (23, X = Ph; 24, X = 1-naphthyl; 25, X = 9-phenantrenyl), respectively. 1-Phenylazagermatrane (23) is transformed to 8 by treatment with n-BuLi/Me3SiCl. Composition and structures of novel compounds were established by elemental analyses, 1H, 13C, and 29Si NMR spectroscopy, and mass spectrometry. The X-ray structural studies of 10 and 19 clearly indicated the presence of a transannular interaction M←Nax for both compounds. quasi-Azametallatranes 5 and 8 possess extremely long M←Nax distances.