| Abstrakt: |
In an attempt to build up borane-based multicluster assemblies, thermolysis of [6,9-(SMe2)2-arachno-B10H12] 1in inert hydrocarbon solution, followed by chromatographic separation, has resulted in the isolation not only of the previously established single-cluster product from this reaction, [5-(SMe2)-nido-B10H12] 2(30%), but also the two two-cluster species [6,9-(SMe2)2-arachno-B10H11-1-(6′-nido-B10H13)] 3(20%) and [1,6′-(nido-B10H13)2] 6(ca.0.5%) and the two three-cluster species [6,9-(SMe2)2-arachno-B10H10-1,5-(6′-nido-B10H13)2] 4(5%), characterized crystallographically, and [6,9-(SMe2)2-arachno-B10H10-1,3-(6′-nido-B10H13)2] 5(<1%), identified by NMR spectroscopy. An improved crystallographic investigation of [5-(SMe2)-nido-B10H12] 2is also presented. The feasibility of the stability of species resulting from multiple adjacent substitution of nido-decaboranyl units on the [6,9-(SMe2)2-arachno-B10H12] skeleton is tested by DFT calculations. In an extension, to attempt the use of pre-σ-linked two-cluster compounds as starting substrates, two-cluster [5-(SMe2)-4-(2′-nido-B10H13)-nido-B10H11] 7(0.6%) has been isolated from the reaction of SMe2with [1,5′-(nido-B10H13)2], other identified products being compound 1(39%) and compound 3(10.5%). |
