The reactions of the dimeric organoantimony(III) oxide [LSbO]2 (3), containing the NCN chelating ligand L (L = C6H3-2,6-(CH2NMe2)2) with trifluoroacetic acid and trifluoromethanesulfonic acid gave the unprecedented organoantimony hydroxides LSb(OH)(X) (X = CF3CO2 (6), CF3SO3 (7)). On the other hand, analogous reactions with acetic acid and tetrafluoroboric acid led to a polar group exchange, providing the compounds LSbX2 (X = F(4), CH3CO2 (5)). Analogously, the organobismuth oxide [LBiO]2 (8) gave the acetate LBi(O2CCH3)2 (9) in its reaction with acetic acid but the hydroxide LBi(OH)(CF3SO3) (10) was obtained when trifluoromethanesulfonic acid was used. All compounds were characterized with the help of elemental analysis, ESI mass spectrometry, and 1H and 13C NMR spectroscopy, and their molecular structures were determined by X-ray diffraction techniques. The molecular structures of hydroxides 6 and 7 may be described as being built up from the organoantimony cation [LSb(OH)]+ effectively stabilized by the NCN ligand L and the counteranion X−, which is connected to the terminal Sb−OH moiety through the hydrogen bond Sb−OH···X. The organobismuth analogue 10 forms the weakly bonded dimeric units LBi(μ-OH)2BiL, and the triflate anions are connected to the bridging OH moieties via the hydrogen bonds as well as to the bismuth centers through Bi−O interactions, leading to an infinite chain supramolecular structure of 10.

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The reaction of YCl3·3.5THF with 1 equiv. of Li(C5Me4SiMe3) afforded in high yield the ionic complex [Li(thf)4]+{[(η5‐C5Me4SiMe3)YCl2]4(µ4‐Cl)}– (1). The molecule of 1 consists of the tetranuclear anion {[(η5‐C5Me4SiMe3)YCl2]4(µ4‐Cl)}– compensated with [Li(thf)4]+ in the solid state. Reactions of compound 1 with selected lithium and potassium cyclopentadienides resulted in the formation of yttrocene chloride complexes [(η5‐C5Me4SiMe3)Y(L)(µ‐Cl)2M(thf)2] [M = Li, L = η5‐C5H5 (2); M = Li, L = η5‐C5Me5 (3); M = Li, L = η5‐C5Me4SiMe2H (4); M = K, L = η5‐C5Me4CH2Ph (5)]. Yttrocene chloride complexes 2–5 underwent methylation reactions to give yttrocene methyl complexes [(η5‐C5Me4SiMe3)Y(L)(µ‐Me)2Li(thf)2] [L = η5‐C5H5 (6); L = η5‐C5Me5 (7); L = η5‐C5Me4SiMe2H (8); L = η5‐C5Me4CH2Ph (9)]. The products of all these reactions were characterized by NMR and IR spectroscopy, and 2–5 were further studied by ESI mass spectrometry. The molecular structures of 1 and 4 were determined by single‐crystal XRD. The methyl‐bridged complexes 6–9 were tested as homogeneous catalysts for ethylene polymerization in the absence of cocatalysts.

The reaction of an N,C,N-intramolecularly coordinated tin(IV) carbonate LSn(Ph)(CO3) (1) and antimony(III) and bismuth(III) oxides (LMO)2 (where M = Sb (2), Bi (3) and L = C6H3-2,6-(CH2NMe2)2) with (HO)SiPh2(O)SiPh2(OH) in 1 : 1 (in the case of 1) or 1 : 2 molar ratio (in the cases of 2 and 3) gave the metallasiloxanes cyclo-LSn(Ph)(OSiPh2)2O (4) and cyclo-LM(OSiPh2)2O (where M = Sb (6) and Bi (7)) containing six-membered MSi2O3 rings. Alternatively, the compounds 4, 6 and 7 can be also prepared reacting Ph2Si(OH)2 and compounds 1, 2 and 3, respectively, in the molar ratio of either 2 : 1 (for 4) or 4 : 1 (for 6 and 7). The reaction of Ph2Si(OH)2 with 1 in 1 : 1 molar ratio gave cyclo-Ph2Si(OSnL(Ph)O)2SiPh2 (5) containing an eight-membered Sn2Si2O4 stannasiloxane ring. The analogous eight-membered stibasiloxane derivative cyclo-Ph2Si(OSbLO)2SiPh2 (8) was obtained as well, while attempts to synthesize the bismuth analogue failed. Compounds 1-3 react with the siloxane cyclo-(Me2SiO)3 providing either eight-membered metallasiloxanes cyclo-LSn(Ph)(OSiMe2O)2SiMe2 (9) and cyclo-LSb(OSiMe2O)2SiMe2 (10) or the six-membered bismutasiloxane cyclo-LBi(OSiMe2)2O (11). All compounds were characterized with the help of elemental analysis, (1)H, (13)C, (29)Si and (119)Sn NMR spectroscopy, and single crystal X-ray diffraction analyses (except 9 and 10).

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