[1]Ferrocenophanes, [1]Chromarenophanes, and [1]Vanadarenophanes with Aluminium and Gallium in Bridging Positions

Abstract

Aluminum- and gallium-bridged [1]ferrocenophanes (4a, 4b), [1]chromarenophanes (5a, 5b), and [1]vanadarenophanes (6a, 6b) were synthesized from the respective dilithiated sandwich compounds with element dichlorides (Me2Ntsi)ECl2 [E = Al, Ga; Me2Ntsi = C(SiMe3)2(SiMe2NMe2)] in moderate to high isolated yields (54−97%). The new intramolecularly stabilized aluminum compound (Me2NCH2tsi)AlCl2 (2a) was synthesized, but was proven to be unreactive with respect to [Fe(LiC5H4)2]·2/3TMEDA. The diamagnetic species 2a, 4a, 4b, 5a, and 5b were characterized by NMR spectroscopy (1H, 13C, 27Al), CHN elemental analysis, and mass spectrometry, whereas the paramagnetic compounds 6a and 6b were characterized by IR spectroscopy, CHN elemental analysis, and mass spectrometry. In addition, the molecular structures of compounds 2a, 4a, 4b, 5a, 5b, 6a, and 6b were determined by single-crystal X-ray analysis. All [1]cyclophanes are strained species, as revealed by the following tilt angles α [deg]: 14.33(14) (4a), 15.83(19) (4b), 11.81(9) (5a), 13.24(13) (5b), 14.65(14) (6a), and 15.63(14) (6b).

Synthesis and Reactivity of Boron‐, Silicon‐, and Tin‐Bridged ansa‐Cyclopentadienyl–Cycloheptatrienyl Titanium Complexes (Troticenophanes)

“…Again, the carbonmetal distances to the seven-membered ring (2.200(5)-2.250(4) ) are significantly shorter than those to the fivemembered ring (2.298(2)-2.302(4) ). As already indicated by 13 C NMR data, both ring ligands adopt an almost coplanar arrangement, which is reflected by the angles a = 0.78 and d = 179.58, and the bridging C and Si atoms exhibit a distorted tetrahedral geometry. The most important geometrical parameters of compounds 4-6 and 8-11 are summarized in Table 2.…”

“…As expected, the incorporation of a triatomic bridge in [Ti(h 5 [43] and show two signals for the C 5 H 4 protons at d = 5.02 and 5.10 ppm and one multiplet for the C 7 H 6 moiety at d = 5.53 ppm. In addition, deshielded resonances of the ipso-carbon atoms are observed in the 13 C NMR spectrum (C 5 H 4 : 110.3 ppm; C 7 H 6 : 94.9 ppm), which is consistent with the unstrained character of 11.…”

“…[8] In contrast to ferrocene, the related chemistry of non-iron metallocenes such as ruthenocene, [9] cobaltocene, [10] and nickelocene, [11] Abstract: A novel one-pot method was developed for the preparation of [Ti-A C H T U N G T R E N N U N G (h (h has not been extensively developed, [10] and the situation is even worse for homoleptic non-metallocene systems, such as bisA C H T U N G T R E N N U N G (benzene)vanadium, [12,13] bisA C H T U N G T R E N N U N G (benzene)chromium, [12f, 13, 14] and bisA C H T U N G T R E N N U N G (benzene)molybdenum, [15] even though these sandwich complexes have been known for decades. Recently, the preparation of strained organometallic complexes has been extended to a new class of sandwich compounds of the formula [MA C H T U N G T R E N N U N G (h …”

Ferrocenyl(dimethyl)aluminum dimer [(η5-C5H5)Fe(η5-C5H4)AlMe2]2

“…Surprisingly little information is available on ferrocenylaluminum compounds. Recently, it has been shown that the reactions of 1,1 0 -dilithiated ferrocene fcLi 2 with organoaluminum dihalides afford ferrocenophanes with aluminum in the bridge, stabilised by intramolecular coordination [5,6], 1,1 0 -disubstituted ferrocene [7] or rather novel types of ferrocenylaluminum compounds [6b,8]. Ferrocenylmercury chloride reacts with trialkylalanes to give mixed dimers 2 [9].…”

The galla[1]ferrocenophane {[dimethyl(2-pyridyl)silyl]bis(trimethylsilyl)methyl-κ2C,N}(ferrocene-1,1′-diyl)gallium(III)

“…A related galla[1]ferrocenophane was published by Lund et al (2006). For related literature, see: Bellas & Rehahn (2007) ;Foucher et al (1992); Herbert et al (2007); Lund et al (2007); Osborne & Whiteley (1975); Schachner et al (2005aSchachner et al ( , 2007.…”