Quadrupole–Dipole Effects in Solid-State, CP-MAS, Tin-119 NMR Spectra ofpara-Substituted Triaryltin(pentacarbonyl)manganese(I) Complexes
✍ Scribed by Dharamdat Christendat; Ivor Wharf; Frederick G. Morin; Ian S. Butler; Denis F.R. Gilson
- Publisher
- Elsevier Science
- Year
- 1998
- Tongue
- English
- Weight
- 171 KB
- Volume
- 131
- Category
- Article
- ISSN
- 1090-7807
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✦ Synopsis
Solid-state, CP-MAS, 119 Sn NMR spectra were measured for a plexes has involved solution studies of the isotropic tin-119 series of para-substituted triaryltin(pentacarbonyl)manganese(I) chemical shifts and spin-spin coupling ( n J C-Sn ) between 13 C complexes. All the spectra show an asymmetric sextet due to spinand 119 Sn, and it has been found that small changes in molecspin coupling and second-order quadrupolar effects, transmitted ular structure can lead to significant changes in both of these by dipolar coupling between the 119 Sn and 55 Mn nuclei, which are parameters (12, 13). These changes have been related to the not suppressed by magic-angle rotation. The solid-state 1 J Mn-Sn electronegativities of the substituents, their sand p-bonding spin-spin and nuclear quadrupole coupling constants range from character, and the coordination state of the tin atom (12). 130 to 250 Hz and 08 to 21 MHz, respectively, and show an
The objective of the present study was to investigate the inverse linear correlation, which is attributed to the dominance of effects of para-substituents on the aryl rings in the solidthe Fermi contact contribution to the 1 J Mn-Sn coupling. The tris( pstate, CP-MAS, 119 Sn NMR spectra of a series of (paramethylthiophenyl)tin derivative is an exception, attributed to a difference in crystal structure from the other complexes. The mag-X C 6 H 4 ) 3 Sn(CO) 5 Mn [X Å H, F, Cl, CH 3 , OCH 3 , SCH 3 , nitudes of the principal elements of the 119 Sn chemical shift tensors and S(O) 2 CH 3 ] derivatives. The specific parameters under were determined and appear to be strongly influenced by the ring investigation were the manganese-tin spin-spin coupling torsion angles and the para-substituents of the phenyl rings. Solidconstants ( 1 J Mn-Sn ), the effective dipolar coupling constants, state 119 Sn NMR spectroscopy provides a useful method of probing and the 55 Mn quadrupole coupling constants. This study prothe electronic environment around the tin and manganese nuclei vides an opportunity to examine the relationship between in transition metal complexes. ᭧ 1998 Academic Press the 1 J Mn-Sn coupling and the nuclear quadrupole coupling constant, x, in these triaryltin(pentacarbonyl)manganese(I) derivatives.