3 years ago

Rare Earth and Main Group Metal Poly(hydrosilyl) Compounds

Rare Earth and Main Group Metal Poly(hydrosilyl) Compounds
Aaron D. Sadow, KaKing Yan, Nicole L. Lampland, Arkady Ellern, Aradhana Pindwal
The potassium poly(hydrosilyl) compound KSi(SiHMe2)3, which contains three β-SiH groups, is synthesized by the reaction of Si(SiHMe2)4 and KOtBu. A single-crystal X-ray diffraction study reveals chains composed of head-to-tail KSi(SiHMe2)3 monomers. This potassium poly(hydrosilyl) anion reacts with divalent metal halide salts in THF to form the bis(silyl) compounds Mg{Si(SiHMe2)3}2THF2 (1·THF2), Ca{Si(SiHMe2)3}2THF3 (2·THF3), and Yb{Si(SiHMe2)3}2THF3 (3·THF3). A trivalent yttrium bis(silyl), as part of a KCl-containing polymeric chain, is supported by K↼H–Si bridging interactions. The N donors pyridine (py) and dimethylaminopyridine (DMAP) readily substitute THF, giving tetrahedral magnesium and octahedral calcium silyl compounds. The one-bond silicon–hydrogen coupling constants (1JSiH), infrared stretching frequencies (νSiH), and solid-state structures of 2·py4 and 3·THF3 indicate classical two center-two electron bonding between the metal center and the silyl ligand, as well as terminal (nonbridging) Si–H bonds within the silyl ligands. The magnesium and calcium compounds readily react with the Lewis acids PhB(C6F5)2 and B(C6F5)3 to give hydridoborate salts, whereas {κ3-ToM}2Yb (5) (ToM = tris(4,4-dimethyl-2-oxazolinyl)phenyl borate) is formed by reaction of TlToM and 3·THF3.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00383

DOI: 10.1021/acs.organomet.7b00383

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