13.13) is isolated in 50% yield from the addition of CS 2 to solutions of an as-yet
unidentified silver 4-tertbutylthiolate polynuclear complex. The core of the discusshaped cluster 18 is asymmetric, with a diameter of 2.0 nm and a maximum
thickness @ 0.7 nm. The oblate nature of the AgS frame may be correlated with the
relatively large number of surface thiolate ligands present on such a high nuclearity cluster complex, with a correspondingly low number (seven) of interstitial S
2À
centers. The thiolate ligands bridge 2, 3 and 4 Ag(I) ions.
The possibility of synthesizing silver sulfide nanoclusters, as demonstrated with
the formation of 18, was followed immediately by the report of the isolation and
characterization of the mixed silver sulfide–thiolate complex [Ag 70 S 16 (SPh) 34 Á
(PhCO 2 ) 4 (triphos) 4 ] (triphos ¼ 1,1,1-tris{(disphenylphosphino)methyl}ethane) [64].
This cluster is accessed using a combination of PhSSiMe 3 , S(SiMe 3 ) 2 and
Fig. 13.12. The molecular structures [Ag 30 Te 9 (TePh) 12 (PEt 3 ) 12 ]
16 (top) and [Ag 46 Te 17 {Te(mes)} 12 (PEt 3 ) 16 ] 17 [58].
13 Large Semiconductor Molecules
434