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

• Published in: Russian chemical bulletin Vol. 68; no. 1; pp. 137 - 148
• Main Authors: Korlyukov, A. A., Arkhipov, D. E., Volodin, A. D., Negrebetskii, Vad. V., Nikolin, A. A., Kramarova, E. P., Shipov, A. G., Baukov, Yu. I.
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.01.2019; Springer Nature B.V
• Subjects: Amino acids; Bonding strength; BROMIDES; BROMINE; CHELATES; CHEMICAL SHIFT; Chemical synthesis; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; CLEAVAGE; Derivatives; ELECTRON DENSITY; Full Articles; Inorganic Chemistry; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; INTERATOMIC DISTANCES; Mathematical analysis; NMR; NUCLEAR MAGNETIC RESONANCE; Organic Chemistry; ORGANIC FLUORINE COMPOUNDS; PROLINE; SARCOSINE; Silicon; SILICON 29; SILICON COMPLEXES; SILICON COMPOUNDS; SULFONATES; TOPOLOGY; X-RAY DIFFRACTION; synthesis; silicon-containing amino acids; X-ray diffraction; quantum chemical calculations; five-coordinate silicon compounds
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-019-2429-z

Derivatives of the amino acids sarcosine and proline – triflates TsN(Me)CH 2 C(O)N(Me)-CH 2 SiMe 2 OTf and Ns–Pro–N(Me)CH2SiMe2OTf (Ns is 4-NO 2 C 6 H 4 SO 2 ) – 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)CH 2 C(O)N(Me) CH 2 SiMe 2 Br 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 29 Si NMR chemical shifts were calculated. The interatomic Si…X interaction in triflate TsN(Me)CH 2 C(O)- N(Me)CH 2 SiMe 2 OTf and bromide TsN(Ac)CH 2 C(O)N(Me)CH 2 SiMe 2 Br is weak. In triflate Ns–Pro–N(Me)CH 2 SiMe 2 OTf and bromide NsNHCH(Me)C(O)N(Me) CH 2 SiMe 2 Br, 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.