Chalcogen substitution effect

Finally, we discuss the effects of chalcogen (S to Se) substitution. Although in (EDS-TTF)2FeBr4 remarkably close Se---Br contacts exist between donor and anion layers, little magnetic exchange interaction exists between the magnetic anions. The molecular orbital calculation reveals that the contribution of Se 4p orbital to the HOMO of the EDS-TTF molecule is considerably smaller than the contribution of... 

In view of the preference of the tetrasilabuta-1,3-diene 139 for the s-cis form, it seemed worthwhile to examine its behavior in [4 + 2] cycloadditions of the Diels-Alder type. Since 139, like many disilenes, should behave as an electron-rich diene, we attempted to react it with various electron-poor and also with some electron-rich olefins. No reaction was detected in any case. Only in the presence of water did 139 react with quinones to furnish the unsymmetrically substituted disilenes 36 and 37 (see Section III.A). The effective shielding of the double bonds by the bulky aryl groups and, above all, the 1, 4-separation of the terminal silicon atoms of about 5.40 A appear to be responsible for these failures. Thus, it was surprising that treatment of 139 with the heavier chalcogens afforded five-membered ring compounds in a formal [4 + 1] cycloaddition (see below). 

Substituent effects on weak noncovalent interactions (pnicogen, chalcogen, and halogen bonding) (2013SC(24)1705) in complexes of X-substituted... 

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