P−H-Functionalized Phosphanyl Alcohols: RHPCH2CHMeOH and 2-PHR-1-OH-cyclo-C6H10 (R = Ph, 2,4,6-Me3C6H2, 2,4,6-iPr3C6H2) and Molecular Structures of (CR,CR,PR/CS,CS,PS)-2-PH(2,4,6-iPr3C6H2)-1-OH-cyclo-C6H10 and its Dilithio Salt [Li2(THF)0.5{(CR,CR/CS,CS)-2-P(2,4,6-iPr3C6H2)-1-O-cyclo-C6H10}]4

Abstract

The P−H‐functionalized phosphanyl alcohols RHPCH2CHMeOH [R = Ph (1), 2,4,6‐Me3C6H2 (Mes) (2), 2,4,6‐iPr3C6H2 (Tipp) (3)] and 2‐PHR‐1‐OH‐cyclo‐C6H10 [(R = Ph (4), Mes (5), Tipp (6)] have been prepared by ring‐opening of propene oxide or cyclohexene oxide, respectively, with the appropriate LiPHR species, followed by hydrolytic workup and distillation (1−4) or recrystallization (5, 6). 1−6, which were obtained as diastereomeric mixtures, have been characterized spectroscopically (1H, 13C, 31P NMR, IR, MS). Only in the case of 6 could separation of the diastereomers be achieved by fractional crystallization and the molecular structure of the racemic isomer (CR,CR,PR/CS,CS,PS) has been determined. In situ double deprotonation of 1−6 with BuLi gave the corresponding dianions 1a−6a. The molecular structure of the dilithio salt [Li2(THF)0.5{(CR,CR/CS,CS)‐2‐P(2,4,6‐iPr3C6H2)‐1‐O‐cyclo‐C6H10}]4 (6a) has been determined and shows that it is tetrameric in the solid state with a central Li8 cluster.

Structure, Conformation, and Dynamics of P,N-Containing Cyclophanes in Solution

“…Frequencies are 600. 13 MHz in 1 H NMR, 242.94 MHz in 31 P NMR, 150.90 MHz in 13 C NMR, and 60.81 MHz in 15 N NMR experiments. Samples (15 mM/L) were prepared by dissolving in 0.6 mL of the corresponding solvent (CDCl 3 , 99.5% D; C 6 D 6 , 99.5% D; toluene-d 8 , 99.5% D (Deiton, Russia)) in inert atmosphere (Ar) and were placed in standard NMR tubes (Norell, USA).…”

“…Synthesis. 1 3 ,1 7 ,7 3 ,7 7 -Tetrakis(2′,4′,6′-triisopropylphenyl)-3,3,5,5,9,9,11,11-octamethyl-1,7(1,5)-bis(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8,10,12(1,4)-hexabenzenacyclododecaphane (1), 1 3 ,1 7 ,7 3 ,7 7 -Tetrakis(mesityl)-3,3,5,5,9,9,11,11octamethyl-1,7(1,5)-bis(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8,10,12 (1,4)-hexabenzenacyclododecaphane (2) 29 and 2,4,6triisopropylphenylphosphine (4) 31 were prepared according to procedures reported previously. 1,4-Bis[R-(4′-aminophenyl)isopropyl]benzene (3) was purchased from TCI Europe NV.…”

Delocalized Bonding in Li2X2Rings: Probing the Limits of the Covalent and Ionic Bonding Models

“…Notice, however, that there is no gap between bonds and no-bonds, suggesting that the existence of Li–Li bonding at distances of 3.0 Å or longer cannot be established based purely on a bond length criterion. A look at the structures that present such Li–Li short distances reveals a strong tendency of lithium atoms to cluster together forming Li 2 X 2 rings, Li 4 R 4 clusters in which the organic groups are linked in a μ 3 fashion to the faces of a Li 4 tetrahedron (R = e.g., Me, t Bu, or CH 2 CH 2 t Bu), six-member rings in a chair conformation, − a Li 8 cube, a Li 8 gyrobifastigium, larger clusters up to Li 37 , reminiscent of a chunk of the bcc structure of metallic lithium but with shorter Li–Li distances (2.74–2.93 Å) than in the metal, and in a square network in lithium cyanamide, Li 2 (NCN) . The most common motifs with Li–Li bonds or short contacts found in the CSD are Li 2 X 2 rings, where the bridging atom X is most frequently C, N, or O but can also be almost any element of groups 14–17, from carbon to iodine.…”

P,N-Containing cyclophanes with large helical hydrophobic cavities: prospective precursors for the design of a molecular reactor

“…hexabenzenacyclododecaphane (1). A mixture of 2,4,6-tris(isopropyl)phenylphosphine11 (0.8 g, 3.4 mmol) and paraformaldehyde (0.2 g, 6.7 mmol) was heated to 110 • C for 3 h, then 15 mL of toluene and 1,4-bis[a-(4¢-aminophenyl)isopropyl]benzene (0.58 g, 1.7 mmol) were added and the reaction mixture was stirred at 80•C for 2 d. The resulting white microcrystals were collected by filtration, washed with acetonitrile, and dried in vacuo. Yield: 0.53 g, 42%; m.p.…”