Effect of Electronic Interactions on NMR 1JCF and 2JCF Couplings in cis- and trans-4-t-Butyl-2-fluorocyclohexanones and Their Alcohol Derivatives

被引:20
作者
Anizelli, Pedro R. [1 ]
Favaro, Denize C. [1 ]
Contreras, Ruben H. [2 ,3 ]
Tormena, Claudio F. [1 ]
机构
[1] Univ Estadual Campinas, Inst Chem, BR-13084971 Campinas, SP, Brazil
[2] Univ Buenos Aires, FCEyN, Dept Phys, Buenos Aires, DF, Argentina
[3] Consejo Nacl Invest Cient & Tecn, IFIBA, RA-1033 Buenos Aires, DF, Argentina
基金
巴西圣保罗研究基金会;
关键词
INTRAMOLECULAR VANDERWAALS INTERACTIONS; HYDROXYMETHYL GROUP CONFORMATION; THROUGH-SPACE TRANSMISSION; C-13; CHEMICAL-SHIFTS; POLARIZATION PROPAGATOR; MOLECULAR-STRUCTURE; ANGULAR-DEPENDENCE; HARTREE-FOCK; CONSTANTS; DFT;
D O I
10.1021/jp202592c
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In order to study the influence of hyperconjugative, inductive, steric, and hydrogen-bond interactions on (1)J(CF) and (2)J(CF) NMR spin-spin coupling constants (SSCCs), they were measured in cis- and trans-4-t-butyl-2-fluorocyclohexanones and their alcohol derivatives. The four isotropic terms of those SSCCs, Fermi contact (FC), spin dipolar (SD), paramagnetic spin-orbit (PSO), and diamagnetic spin-orbit (DSO), were calculated at the SOPPA(CCSD)/EPR-III level. Significant changes in FC and PSO terms along that series of compounds were rationalized in terms of their transmission mechanisms by employing a qualitative analysis of their expressions in terms of the polarization propagator formalism. The PSO term is found to be sensitive to proximate interactions like steric compression and hydrogen bonding; we describe how it could be used to gauge such interactions. The FC term of (2)J(CF) SSCC in cis- 4-t-butyl-2-fluorocyclohexanone is rationalized as transmitted in part by the superposition of the F and O electronic clouds.
引用
收藏
页码:5684 / 5692
页数:9
相关论文
共 68 条
[1]  
Angeli C., 2005, DALTON ELECT STRUCTU
[2]  
[Anonymous], 1998, ENCY COMPUTATIONAL C
[3]   Substituent effects on scalar 2J(19F,19F) and 3J(19F,19F) NMR couplings:: A comparison of SOPPA and DFT methods [J].
Barone, V ;
Provasi, PF ;
Peralta, JE ;
Snyder, JP ;
Sauer, SPA ;
Contreras, RH .
JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (23) :4748-4754
[4]   DFT calculation of NMR JFF spin-spin coupling constants in fluorinated pyridines [J].
Barone, V ;
Peralta, JE ;
Contreras, RH ;
Snyder, JP .
JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (23) :5607-5612
[5]   INCLUSION OF HARTREE-FOCK EXCHANGE IN DENSITY-FUNCTIONAL METHODS - HYPERFINE-STRUCTURE OF 2ND ROW ATOMS AND HYDRIDES [J].
BARONE, V .
JOURNAL OF CHEMICAL PHYSICS, 1994, 101 (08) :6834-6838
[6]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[8]  
BERNARD C, 1976, B SOC CHIM FR, P145
[9]   13C13C NMR spin-spin coupling constants in saccharides:: Structural correlations involving all carbons in aldohexopyranosyl rings [J].
Bose-Basu, Bidisha ;
Klepach, Thomas ;
Bondo, Gail ;
Bondo, Paul B. ;
Zhang, Wenhui ;
Carmichael, Ian ;
Serianni, Anthony S. .
JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (20) :7511-7522
[10]   C-13-H-1 and C-13-C-13 spin-coupling constants in methyl beta-D-ribofuranoside and methyl 2-deoxy-beta-D-erythro-pentofuranoside: Correlations with molecular structure and conformation [J].
Church, TJ ;
Carmichael, I ;
Serianni, AS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (38) :8946-8964