6 Group 13–15 Needle-Shaped Oligomers and Nanorods: Structures. . .
211
Scheme 6.4 Reaction pathways, leading to DA stabilized cubanes and higher oligomers according to [48]. (Reprinted with permission from [48]. Copyright 2009 American Chemical Society)
Fig. 6.4 Molecular structure
of donor-acceptor stabilized
ladder
(NMe 3 ) 3 [(HAl) 2 AlP(PH) 2 ]
{W(CO) 5 } 3 compound.
(From [74] Copyright © 2009
by John Wiley Sons, Inc.
Reprinted by permission of
John Wiley & Sons, Inc.)
adamantane-type [(AlX) 4 (NMe 2 ) 4 (NMe) 2 ] cages [102, 103]. In these compounds
the Me groups of amine nitrogen are transferred to the nitrogen atoms of the cluster
core (Fig. 6.5).
Analogous gallium compound [(GaPh) 4 (NH i Bu) 4 (N i Bu) 2 ] which also features
adamantane-type structure has been prepared by reaction of [PhGa(NMe 2 ) 2 ] 2 with
NH 2
i Bu [104]. Noteworthy, that in the chemical ionization mass spectrum at ca
310 ◦ C, the base peak was assigned to [PhGaN i Bu] 4 , suggesting that conversion
of adamantane-type to cubane-type structure occurs at elevated temperatures.
Formation of Ga 4 -containing species was also evidenced in chemical ionization
mass spectrum of [ n HxGa(NMe 2 ) 2 ] 2 at 300 ◦ C [105].
Computational studies of the products of interaction of [HGaNH] 4 with
one and two ammonia molecules suggest that formation of adamantane-type
[(GaH) 4 (NH 2 ) 4 (NH) 2 ] cage is energetically very favorable at low temperatures.