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A. V. Pomogaeva and A. Y. Timoshkin
Formation of incomplete needle-shaped decamer structure [(InMe) 9 (As t Bu) 8
(OH) 2 ]2.5THF was reported by Neumüller [120]. Intermediate formation of zincblende InP cluster fragments, with external faces terminated by residual In- t Bu and
P-H groups, was discussed in [96]. Formation of polymeric material [ClInPSiMe 3 ] n
was observed in reaction of InCl 3 with P(SiMe 3 ) 3 at 150 ◦ C [121]. On further
heating (650 ◦ C), polymeric material was converted to InP. Insoluble residues of
[ t BuGaYH] n (Y=P,As) have been produced by reaction of Ga t Bu 3 and YH 3 [122].
No further characterization of oligomers/polymers has been made.
Computational studies indicate that formation of gas phase needle-shaped clusters from the corresponding hydrides
MH 3 + YH 3 =
1 / n [HMYH] n + 2H 2
is favorable thermodynamically for all 13–15 pairs even at high temperatures
[45, 53].
Stability of the needle-shaped (Fig. 6.8a, c, e) versus fullerene-like (Fig. 6.8b, d,
e) isomers of [HGaNH] n (n=10,13,16) was discussed in [53]. Needle-like isomers
are predicted to be more stable compared to fullerene-like cage structures, and
their stability increases with the increase of the oligomerization degree n [53].
This result has been generalized for all [HMYH] n compounds (M=Al,Ga,In;
Fig. 6.8 Structures of needle-shaped and fullerene-like [HMYH] n isomers. (Reprinted with
permission from [23]. Copyright 2005 American Chemical Society)