TY - JOUR
T1 - Aggregation of Metalated Organics by Hydrogen Bonding
T2 - Synthesis and Crystal Structures of 2-Aminophenoxy-Aluminum and Salen-Aluminum Ligand-Separated Ion Pairs
AU - Davidson, Matthew G.
AU - Lambert, Christoph
AU - Lopez-Solera, Isabel
AU - Raithby, Paul R.
AU - Snaith, Ronald
PY - 1995/7/1
Y1 - 1995/7/1
N2 - Ion separation of Al(2-H2NC6H4O)2Cl and of Al(salen)X [X− = Cl−, I−, CF3SO3−; H2salen = N.N-bis-(salicylidene)ethylenediamine] is promoted by the addition of the strong Lewis base HMPA (hexamethylphos-phoramide) which stabilizes the resulting cationic aluminum species. The X-ray structure of [Al(2-H2-NC6H4O)2(HMPA)2]+Cl− (2a) shows it to be a dimer formed by two [Al(2-H2NC6H4O)2(HMPA)2]+ cations connected via two NH hydrogen bonded Cl− ions. [Al(salen)(HMPA)2]+Cl− (4a) and [Al(salen)(HMPA)2]+CF3SO3− (7a) also form dimeric aggregates but by CH⋯X hydrogen bonds between the salen imine and ethylene protons and the anions, X−. In contrast to the Cl− and CF3SO3− derivatives, [Al(salen)(HMPA)2]+I− (9) forms a three-dimensional ionic lattice structure rather than distinct aggregates. If [AlCl4]− is used as the counterion the weakly Lewis-basic THF is sufficient to stabilize the aluminum cation, as demonstrated by the structure of [Al(salen)(THF)2]+[AlCl4]− (10). This compound also forms an ionic lattice-type structure. The crystal data are as follows. 2a: Cl2H24Alo.5Clo.5N4O2P, orthorhombic, Pnnm; a = 14.675(3), b = 15.059(3), c = 15.132(3) Å; Z = 8. 4a: C56H100Al2Cl2N16O8P4C4H8O, triclinic, P1; a = 10.821(2), b = 11.234(2), c = 32.974(7) Å; α = 84.99(3), β = 82.73(3), γ = 81.38(3)°; Z = 2. 7a: C29H50AlF3N8O7P2S·C7H8, monoclinic, C2/c; a = 29.591-(6), b = 17.102(3), c = 18.018(4) Å, β = 97.98(3)·; Z = 8. 9: C56H100Al2I2N16O8P4, monoclinic, Pn; a = 10.552(2), b = 26.060(5), c = 14.030(3) Å, β = 104.39(3)°; Z = 2. 10: C24H30Al2Cl4N2O4, monoclinic, C2/c; a = 28.474(6), b = 13.896(3), c = 15.532(3) Å; β = 111.80(3)°, Z = 8.
AB - Ion separation of Al(2-H2NC6H4O)2Cl and of Al(salen)X [X− = Cl−, I−, CF3SO3−; H2salen = N.N-bis-(salicylidene)ethylenediamine] is promoted by the addition of the strong Lewis base HMPA (hexamethylphos-phoramide) which stabilizes the resulting cationic aluminum species. The X-ray structure of [Al(2-H2-NC6H4O)2(HMPA)2]+Cl− (2a) shows it to be a dimer formed by two [Al(2-H2NC6H4O)2(HMPA)2]+ cations connected via two NH hydrogen bonded Cl− ions. [Al(salen)(HMPA)2]+Cl− (4a) and [Al(salen)(HMPA)2]+CF3SO3− (7a) also form dimeric aggregates but by CH⋯X hydrogen bonds between the salen imine and ethylene protons and the anions, X−. In contrast to the Cl− and CF3SO3− derivatives, [Al(salen)(HMPA)2]+I− (9) forms a three-dimensional ionic lattice structure rather than distinct aggregates. If [AlCl4]− is used as the counterion the weakly Lewis-basic THF is sufficient to stabilize the aluminum cation, as demonstrated by the structure of [Al(salen)(THF)2]+[AlCl4]− (10). This compound also forms an ionic lattice-type structure. The crystal data are as follows. 2a: Cl2H24Alo.5Clo.5N4O2P, orthorhombic, Pnnm; a = 14.675(3), b = 15.059(3), c = 15.132(3) Å; Z = 8. 4a: C56H100Al2Cl2N16O8P4C4H8O, triclinic, P1; a = 10.821(2), b = 11.234(2), c = 32.974(7) Å; α = 84.99(3), β = 82.73(3), γ = 81.38(3)°; Z = 2. 7a: C29H50AlF3N8O7P2S·C7H8, monoclinic, C2/c; a = 29.591-(6), b = 17.102(3), c = 18.018(4) Å, β = 97.98(3)·; Z = 8. 9: C56H100Al2I2N16O8P4, monoclinic, Pn; a = 10.552(2), b = 26.060(5), c = 14.030(3) Å, β = 104.39(3)°; Z = 2. 10: C24H30Al2Cl4N2O4, monoclinic, C2/c; a = 28.474(6), b = 13.896(3), c = 15.532(3) Å; β = 111.80(3)°, Z = 8.
UR - http://www.scopus.com/inward/record.url?scp=0001341740&partnerID=8YFLogxK
U2 - 10.1021/ic00118a026
DO - 10.1021/ic00118a026
M3 - Article
AN - SCOPUS:0001341740
SN - 0020-1669
VL - 34
SP - 3765
EP - 3779
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 14
ER -