A gr e at d e al of i nt er e st s urr o u n d s t h e u s e of tr a n s cr a ni al dir e ct c urr e nt sti m ul ati o n (t D C S) t o a u g m e nt c o g niti v e tr ai ni n g. H o w e v er, eff e ct s ar e i n c o n si st e nt a cr o s s st u di e s, a n d m et aa n al yti c e vi d e n c e i s mi x e d, e s p e ci all y f o r h e alt h y, y o u n g a d ult s. O n e m aj or s o ur c e of t hi s i n c o n si st e n c y i s i n di vi d u al diff er e n c e s a m o n g t h e pmore »
Origin of the 29 Si NMR chemical shift in R 3 Si–X and relationship to the formation of silylium (R 3 Si + ) ions
The origin in deshielding of 29 Si NMR chemical shifts in R 3 Si–X, where X = H, OMe, Cl, OTf, [CH 6 B 11 X 6 ], toluene, and O X (O X = surface oxygen), as well as i Pr 3 Si + and Mes 3 Si + were studied using DFT methods. At the M06-L/6-31G(d,p) level of theory the geometry optimized structures agree well with those obtained experimentally. The trends in 29 Si NMR chemical shift also reproduce experimental trends; i Pr 3 Si–H has the most shielded 29 Si NMR chemical shift and free i Pr 3 Si + or isolable Mes 3 Si + have the most deshielded 29 Si NMR chemical shift. Natural localized molecular orbital (NLMO) analysis of the contributions to paramagnetic shielding ( σ p ) in these compounds shows that Si–R (R = alkyl, H) bonding orbitals are the major contributors to deshielding in this series. The Si–R bonding orbitals are coupled to the empty p-orbital in i Pr 3 Si + or Mes 3 Si + , or to the orbital in R 3 Si–X. This trend also applies to surface bound R 3 Si–O X . This model also more »
- Award ID(s):
- 1800561
- Publication Date:
- NSF-PAR ID:
- 10227736
- Journal Name:
- Dalton Transactions
- Volume:
- 49
- Issue:
- 45
- Page Range or eLocation-ID:
- 16453 to 16463
- ISSN:
- 1477-9226
- Sponsoring Org:
- National Science Foundation
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