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EnglishThe synthesis and characterization of the new macrobicyclic cage 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.4]hexadecane L is reported. Its basicity behaviour in aqueous solution has been investigated by potentiometric (25 °C, I= 0.15 mol dm–3) and NMR (1H and 13C) techniques. It behaves as a very strong base (proton sponge) in the first protonation step, and as a moderate base in the second step (log K2= 7.8). 1H–1H and 1H–13C two-dimensional NMR experiments permitted the unequivocal assignment of all 1H proton and 13C resonances of both species HL+ and H2L2+. Furthermore NMR experiments indicate that the first protonation involves the bridgehead nitrogens. Crystals of [HL][ClO4] are orthorhombic, space group P21cn, with a= 9.044(2), b= 12.573(2), c= 16.126(3)Å, and Z= 4; final R value of 0.089 (Rw= 0.086) for 1267 unique observed reflections with I > 3σ(I). X-Ray analysis shows that protonation occurs on the bridgehead nitrogen N(2) and an overall macrocyclic conformation with the all nitrogen atoms in the endoconfiguration. The short H(2)(4)[1.69(1)Å] and N(2) N(4)[2.75(1)Å] distances indicate a strong hydrogen bond. H(2) further interacts with the other two tertiary nitrogens: H(2) N(1)[2.53(1)Å] and H(2) N(3)[2.46(1)Å]. This arrangement makes the monoprotonated species very stable from the thermodynamic point of view and explains the high basicity of L. Crystals of [H3L][ClO4]3 are tetragonal, space group P43212, with a= 8.498(2), b= 8.498(2), c= 32.855(8)Å, and Z= 4; final R value of 0.083 (Rw= 0.093) for 1076 unique observed reflections with I > 3σ(I). The X-ray analysis shows an overall macrocyclic conformation with two nitrogen atoms in the endoconfiguration and two in exo configuration.
Synthesis and Chracterization of an Aza-cage Behaving as a 'Proton Sponge'. Crystal Structures of its Mono- and Tri-protonated Species / A.Bencini; A.Bianchi; C.Bazzicalupi; M.Ciampolini; P.Dapporto; V.Fusi; M.Micheloni; N.Nardi; P.Paoli; B.Valtancoli. - In: JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS II. - ISSN 0300-9580. - STAMPA. - ...(1993), pp. 115-120.
| Titolo: | Synthesis and Chracterization of an Aza-cage Behaving as a 'Proton Sponge'. Crystal Structures of its Mono- and Tri-protonated Species | |
| Autori di Ateneo: | ||
| Autori: | BENCINI, ANDREA; BIANCHI, ANTONIO; BAZZICALUPI, CARLA; M. Ciampolini; P. Dapporto; V. Fusi; M. Micheloni; N. Nardi; PAOLI, PAOLA; VALTANCOLI, BARBARA | |
| Data di pubblicazione: | 1993 | |
| Rivista: | ||
| Volume: | ... | |
| Pagina iniziale: | 115 | |
| Pagina finale: | 120 | |
| Abstract: | The synthesis and characterization of the new macrobicyclic cage 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.4]hexadecane L is reported. Its basicity behaviour in aqueous solution has been investigated by potentiometric (25 °C, I= 0.15 mol dm–3) and NMR (1H and 13C) techniques. It behaves as a very strong base (proton sponge) in the first protonation step, and as a moderate base in the second step (log K2= 7.8). 1H–1H and 1H–13C two-dimensional NMR experiments permitted the unequivocal assignment of all 1H proton and 13C resonances of both species HL+ and H2L2+. Furthermore NMR experiments indicate that the first protonation involves the bridgehead nitrogens. Crystals of [HL][ClO4] are orthorhombic, space group P21cn, with a= 9.044(2), b= 12.573(2), c= 16.126(3)Å, and Z= 4; final R value of 0.089 (Rw= 0.086) for 1267 unique observed reflections with I > 3σ(I). X-Ray analysis shows that protonation occurs on the bridgehead nitrogen N(2) and an overall macrocyclic conformation with the all nitrogen atoms in the endoconfiguration. The short H(2)(4)[1.69(1)Å] and N(2) N(4)[2.75(1)Å] distances indicate a strong hydrogen bond. H(2) further interacts with the other two tertiary nitrogens: H(2) N(1)[2.53(1)Å] and H(2) N(3)[2.46(1)Å]. This arrangement makes the monoprotonated species very stable from the thermodynamic point of view and explains the high basicity of L. Crystals of [H3L][ClO4]3 are tetragonal, space group P43212, with a= 8.498(2), b= 8.498(2), c= 32.855(8)Å, and Z= 4; final R value of 0.083 (Rw= 0.093) for 1076 unique observed reflections with I > 3σ(I). The X-ray analysis shows an overall macrocyclic conformation with two nitrogen atoms in the endoconfiguration and two in exo configuration. | |
| Handle: | http://hdl.handle.net/2158/6019 | |
| Appare nelle tipologie: | 1a - Articolo su rivista |
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