Aggregation and Solvation of Chiral N,P-Amide Ligands in Coordinating Solvents: A Computational and NMR Spectroscopic Study

被引：8
|
作者：
Ronnholm, Petra [1 ]
Lill, Sten O. Nilsson [1 ]
Grafenstein, Jurgen [1 ]
Norrby, Per-Ola [1 ]
Pettersson, Mariell [1 ]
Hilmersson, Goran [1 ]
机构：
[1] Univ Gothenburg, Dept Chem & Mol Biol, S-41296 Gothenburg, Sweden
来源：
CHEMPLUSCHEM | 2012年 / 77卷 / 09期
关键词：
aggregation; density functional calculations; lithium; NMR spectroscopy; N; P ligands; MOLECULAR-ORBITAL METHODS; TRANSITION-METAL-COMPLEXES; GAUSSIAN-TYPE BASIS; ASYMMETRIC ADDITION; LITHIUM AMIDE; AB-INITIO; SUBSTITUTION ENERGIES; DFT METHODS; ENANTIOSELECTIVE ADDITION; CHEMICAL-SHIFTS;
D O I：
10.1002/cplu.201200033
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The lithium amides of a series of chiral N,P ligands were studied in solution. This ligand class had been shown previously to give good selectivities in asymmetric alkylation of benzaldehyde. These lithium amides were found to aggregate into dimers with surprisingly strong coordination of phosphorus to lithium. The equilibrium between dimeric forms was found to depend strongly on non-bonded interactions within the solute and between solute and solvent. Only if dispersion and free-energy contributions were scaled to approximately 20?% of the gas-phase values was it possible to reproduce the experimentally observed aggregation preferences. NMR spectroscopic shieldings were calculated and found to correlate well with the experimentally observed shifts. Calculated Li,P couplings were shown to be a sensitive measure of the Li?P distance.
引用
收藏
页码：799 / 806
页数：8
相关论文
共 50 条
  • [21] Platinum(II) Complexes of Cyclic Triphosphenium Ions: a 31P NMR Spectroscopic and Computational Study
    Coffer , Philippa K.
    Deng, Robert M. K.
    Dillon, Keith B.
    Fox, Mark A.
    Olivey, Richard J.
    INORGANIC CHEMISTRY, 2012, 51 (18) : 9799 - 9808
  • [22] Determination of the N-methyl stereochemistry in tropane and granatane derivatives in solution: a computational and NMR spectroscopic study
    Lazny, Ryszard
    Ratkiewicz, Artur
    Nodzewska, Aneta
    Wynimko, Anna
    Siergiejczyk, Leszek
    TETRAHEDRON, 2012, 68 (31) : 6158 - 6163
  • [23] 3-aminopyrrolidine lithium amides as chiral ligands for alkyllithium derivatives:: Synthesis, NMR analysis, and computational study of their mixed aggregates
    Harrison-Marchand, A
    Valnot, JY
    Corruble, A
    Duguet, N
    Oulyadi, H
    Desjardins, S
    Fressigné, C
    Maddaluno, J
    PURE AND APPLIED CHEMISTRY, 2006, 78 (02) : 321 - 331
  • [24] Study of Solvation Behavior Thermodynamics and FT-IR Spectroscopic Analysis of N-Butylethanolammonium Based Ionic Liquids with Polar Solvents
    Losetty, Venkatramana
    Yadav, C. Hazarathaiah
    Aswini, K.
    Kumar, Ch Bharath
    Sivakumar, K.
    JOURNAL OF MOLECULAR STRUCTURE, 2022, 1254
  • [25] SPECTROSCOPIC STUDIES OF IONIC SOLVATION .21. RAMAN, INFRARED, AND NMR-STUDY OF SODIUM-PERCHLORATE SOLUTIONS IN NON-AQUEOUS SOLVENTS
    GREENBERG, MS
    POPOV, AI
    JOURNAL OF SOLUTION CHEMISTRY, 1976, 5 (09) : 653 - 665
  • [26] Crystallographic and 6Li and 15N NMR studies of a chiral bidentate lithium amide. An effect of aggregation states on an enantioselective deprotonation reaction
    1600, (114):
  • [27] CRYSTALLOGRAPHIC AND LI-6 AND N-15 NMR-STUDIES OF A CHIRAL BIDENTATE LITHIUM AMIDE - AN EFFECT OF AGGREGATION STATES ON AN ENANTIOSELECTIVE DEPROTONATION REACTION
    SATO, D
    KAWASAKI, H
    SHIMADA, I
    ARATA, Y
    OKAMURA, K
    DATE, T
    KOGA, K
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (02) : 761 - 763
  • [28] Comments on "study of solvation behavior thermodynamics and FT-IR spectroscopic analysis of N-butylethanolammonium based ionic liquids with polar solvents"
    Acree, William E.
    JOURNAL OF MOLECULAR STRUCTURE, 2022, 1262
  • [29] SYNTHESIS AND CHARACTERIZATION OF NEW CHIRAL RH(I) COMPLEXES WITH N,N'-LIGANDS AND N,P-LIGANDS - A STUDY OF ANCHORING ON THE MODIFIED ZEOLITES AND CATALYTIC PROPERTIES OF HETEROGENIZED COMPLEXES
    CARMONA, A
    CORMA, A
    IGLESIAS, M
    SANJOSE, A
    SANCHEZ, F
    JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1995, 492 (01) : 11 - 21
  • [30] A 31P{1H} NMR Spectroscopic Study of Phosphorus-Donor Ligands and Their Transition Metal Complexes
    Cagle, Ethan C.
    Totsch, Timothy R.
    Erdmann, Mitzy A.
    Gray, Gary M.
    JOURNAL OF CHEMICAL EDUCATION, 2018, 95 (06) : 1054 - 1059
12345