Mono-C,O-chelated bromo- and triflatosilanes with an amino acid moiety: salts or covalently bonded complexes?

Abstract

Derivatives of the amino acids sarcosine and proline – triflates TsN(Me)CH₂C(O)N(Me)-CH₂SiMe₂OTf and Ns–Pro–N(Me)CH2SiMe2OTf (Ns is 4-NO₂C₆H₄SO₂) – were synthesized by the reaction of trimethylsilyl triflate with halosilanes prepared previously. Bromide NsNHCH(Me)C(O)N(Me)CH2SiMe2Br was synthesized by the cleavage of the Si–O–Si moiety of the appropriate disiloxane with excess acetyl bromide. The X-ray diffraction study of these compounds and of the previously characterized bromide TsN(Ac)CH₂C(O)N(Me) CH₂SiMe₂Br showed that the Si–O coordination bond lengths in the triflates are 1.7692(14)– 1.8623(14) Å. The interatomic distances between the bromine and silicon atoms are 2.7095(8) and 2.9704(7) Å, which indicates that these bonds are weak. To elucidate the nature of Si…X bonding (X = OTf, Br), the topological analysis of electron density was performed and ²⁹Si NMR chemical shifts were calculated. The interatomic Si…X interaction in triflate TsN(Me)CH₂C(O)- N(Me)CH₂SiMe₂OTf and bromide TsN(Ac)CH₂C(O)N(Me)CH₂SiMe₂Br is weak. In triflate Ns–Pro–N(Me)CH₂SiMe₂OTf and bromide NsNHCH(Me)C(O)N(Me) CH₂ SiMe₂Br, the Si…X interaction is significantly stronger and corresponds to a weak coordination bond. Hence, the tosylates can be considered as salts, whereas the para-nitrobenzenesulfonyl derivatives are monochelated five-coordinate silicon complexes.