N-Aryl-substituted 5-aza-2,8-dioxasilabicyclo[3.3.01.5]octanes: syntheses, molecular structures, DFT calculations and cyclovoltammetric studies

Abstract

The reaction of the silanes X 2 SiCl 2 (X = H, Cl) with the dilithium salts of N -phenyldiethanolamine ( 1 ) and N -4-fl uorophenyl-di-(2-dimethylpropan-2-ol)amine ( 2 ), respectively, gave the novel 5-aza-2,8-dioxasilabicyclo[3.3.0 1.5 ] octanes RN(CH 2 CR ′ 2 O) 2 SiX 2 ( 3 , R = Ph, R ′ = X = H; 4 , R = Ph, R ′ = H, X = Cl; 5 , R = 4-FC 6 H 4 , R ′ = Me, X = H). These compounds were characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction analysis ( 1 -4 ). The molecular structures of the dialkanolamines 1 and 2 are characterized by intra-and intermolecular O-H … O(H) hydrogen bridges giving rise to formation of eight-membered O 4 H 4 rings ( 1 ) and polymeric chains ( 2 ). The 5-aza-2,8-dioxasilabicyclo[3.3.0 1.5 ] octanes show intramolecular N → Si interactions at distances of 2.961(2) ( 3 ) and 2.970(2) ( 4 ) Å , respectively. Also reported is the molecular structure of the hexachloridostannate salt [Ph(H)N(CH 2 CH 2 OH) 2 ] 2 SnCl 6 ( 6a ) that was serendipitously obtained from the reaction of compound 3 with Ph 3 CSnCl 5 under non-inert reaction conditions. Furthermore, DFT calculations on 3 and 4 as well as cyclovoltammetric studies were performed.

CisversusTrans: The Coordination Environment about the Tin(IV) Atom in Spirocyclic Amino Alcohol Derivatives

“…The reaction of Sn(O t Bu) 4 with the symmetrically substituted amino alcohols n BuN(CH 2 CMe 2 OH) 2 ( B ), p ‐FC 6 H 4 N(CH 2 CMe 2 OH) 2 ( C ) as well as the amino alcohol 1 gave spirocyclic compounds 7 – 9 , respectively (Scheme ). These compounds are colourless crystalline materials that show good solubility in common organic solvents such as toluene, dichloromethane and THF.…”

“…The reaction of Sn(O t Bu) 4 with the symmetrically substituted amino alcohol p ‐FC 6 H 4 N(CH 2 CMe 2 OH) 2 ( C ) gave, as a by‐product, a small amount of p ‐FC 6 H 4 N(CH 2 CMe 2 O) 2 Sn(O t Bu) 2 ( 9 a ) as colourless crystalline material. It shows a similar solubility in organic solvents as compound 9 .…”

“…Especially the coordination mode about the tin atom and the strength of the intramolecular N→Sn coordination as a function of the identity of the substituents R and R′ were studied . With growing environmental awareness, nontoxic inorganic tin compounds lacking any tin–carbon bonds are in the focus of research . Amino alcoholate derivatives of tin are such inorganic compounds.…”

The amino alcohol MeN(CH2CMe2OH)2

“…The structure resembles those of Ph(Me)(H)CN(CH 2 CMe 2 OH) 2 (Churakov et al, 2009) and p-FC 6 H 4 N(CH 2 CMe 2 OH) 2 (Lutter et al, 2012). A graph-set analysis according to Bernstein (Bernstein et al, 1990, 1995;Bernstein, 1991;Etter, 1990Etter, , 1991Etter et al, 1990) gives the unitary graph set N 1 = S(8)DS(8)D.…”

“…Some representatives of these compounds have also characterized by single-crystal X-ray diffraction analysis (Churakov et al, 2009). In the context with our long-standing interest in tin and silicon derivatives of amino alcohols (Berends et al, 2009;Glowacki et al, 2016Glowacki et al, , 2017Gock et al, 2013;Iovkova-Berends, Berends, Zö ller, Schollmeyer et al, 2012;Lutter et al, 2012;Zö ller et al, 2011Zö ller et al, , 2012Zö ller & Jurkschat, 2013), we report here the crystal structure of the title compound (Fig. 1).…”