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Synthesis and Crystal Structure of the two Lithium Hypersilylcuprates LiCu2[Si(SiMe3)3]3 and [Li7(OtBu)6][Cu2{Si(SiMe3)3}3]

✍ Scribed by Karl Wilhelm Klinkhammer

Publisher
John Wiley and Sons
Year
2000
Tongue
German
Weight
153 KB
Volume
626
Category
Article
ISSN
0372-7874

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✦ Synopsis

The two hypersilylcuprates LiCu 2 Hyp 3 (2) and [Li 7 (O t Bu) 6 ][Cu 2 Hyp 3 ] (3) (Hyp = Si(SiMe 3 ) 3 ) were synthesized by reactions of unsolvated lithium hypersilanide, Li-Hyp with hypersilylcopper and CuO t Bu, respectively. Both contain the novel A-frame trihypersilyldicuprate anion [Cu 2- Hyp 3 ] Β± . In the former case a molecular compound is produced containing intimate ion pairs. In the latter case the cuprate anion and the unique large [Li 7 (O t Bu) 6 ] + cation form a salt-like compound, only sparingly soluble in unpolar solvents. According to NBO analyses the bonding within the trihypersilyldicuprate moiety is best described by interaction of a bridging lewis-basic hypersilanide anion with two lewisacidic hypersilyl copper fragments.

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The iminophosphane (Me 3 Si) 3 CΟͺP=NΟͺMes\* (1) reacts with Chlorine/bromine exchange in 3 with bromotrimethylsilane affords the bromo analogue 4. The structures of 2, 3 and 4 iodine to form the imino(methylene)phosphorane IΟͺP-(=NΟͺMes\*)=C(SiMe 3 ) 2 (2). Upon subsequent treatment with were confirmed