In:
Chemistry – A European Journal, Wiley, Vol. 11, No. 21 ( 2005-10-21), p. 6392-6406
Abstract:
We report herein a comprehensive study of photoinduced reactions in complexes of Mg + with primary ( n ‐propyl‐ and isopropylamine) and secondary amines (dipropyl‐ and diisopropylamine) in the spectral range of 230–440 nm. Similar to the methyl‐ and ethylamine complexes studied previously, NH bond activation of these complexes is very unfavorable. Instead, the C α C, CN, and C α H bond‐cleavage photoproducts are observed after photoexcitation of the Mg + complexes (3 2 P←3 2 S). For Mg + (primary amine) complexes, for example, Mg + NH 2 CH 2 CH 2 CH 3 , and Mg + NH 2 CH(CH 3 ) 2 , the photoproducts resulting from C α C rupture prevail after P z and charge‐transfer excitations, whereas the Mg + photofragment is predominant upon P x , y excitation. However, with further N ‐alkyl substitution, as in Mg + (secondary amine) complexes, for example, Mg + NH(CH 2 CH 2 CH 3 ) 2 and Mg + NH[CH(CH 3 ) 2 ] 2 , a novel intracomplex CC coupling photoreaction dominates on P x , y excitation of Mg + , which is believed to arise from Mg + * insertion into the CN bond. With P z and charge‐transfer excitation, the MgR elimination photoproducts, arising from C α C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.200401325
Language:
English
Publisher:
Wiley
Publication Date:
2005
detail.hit.zdb_id:
1478547-X
Permalink