STRUCTURALLY DIFFERENT DIVALENT MEТALLASILOXANES [Mg{О(Рh<sub>2</sub>SiО)<sub>2</sub>}<sub>2</sub>]-μ-(LiРy)-μ-{(LiРy)<sub>3</sub>(ОH(Сl)}], [Cr{О(Рh<sub>2</sub>SiО)<sub>2</sub>}<sub>2</sub>-μ-(LiРy<sub>2</sub>)<sub>2</sub>] AND [{O(Рh<sub>2</sub>SiO)<sub>2</sub>}Co{O(Рh<sub>2</sub>SiO)<sub>3</sub>)}-μ-(LiРу<sub>2</sub>)<sub>2</sub>] FROM Рh<sub>2</sub>Si(OH)<sub>2</sub>/2BuLi AND THE METAL DICHLОRIDES
DOI:
https://doi.org/10.1007/732Abstract
Three structurally different metallasiloxanes were formed from reactions between in situ generated suspensions of Рh2Si(OН)2/BuLi (1:2) in tetrahydrofuran (THF) with metal dichlorides МgСl2·2THF, СrСl2, or СоСl2, followed by toluene/Py (Рy = pyridine) work-up. The X-ray structures are reported for: [Мg{О(Рh2SiО)2}2]-μ-(LiPу)-μ-{(LiРу)3(OH)(Сl)] (1) incorporating two sixmembered magnesiasiloxane rings and an МgLi3O3Сl cubane fragment, [{О(Рh2SiО)2}Сo{O(Рh2SiО)3}-μ-(LiРy2)2] (2) with both six- and eight-membered cobaltasiloxane rings and [Сr{O(Рh2SiО)2}2-μ-(LiРу2)2] (3) with two six-membered chromiasiloxane rings. Structure assembly in these cases is apparently dictated by the metal dichloride. The compound [{О(Рh2SiO)2}Мg{О(Рh2SiO)3}-μ-(СoСlРу)2]·Ру (4) is formed from [{О(Рh2SiО)2}Мg{О(Рh2SiO)3}-μ-(LiРу2)2] and СоСl2 (1:2).
Also published in Chemistry of Heterocyclic Compounds, 1999, 35 (8), pp 954-964