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Recent results are summarized on some new aspects of the main group chemistry of the 1,2- diselenido-1,2-dicarba-closo-dodecaborane(12) dianion 3, (1,2-(1,2-C2B10H10)Se2) 2- . The reactions of 3 with organoelement-Group 14 dichlorides (Ph2CCl2, Me2SiCl2, Ph2SiCl2, Me2SnCl2, Ph2SnCl2) and phenylphosphorus dichloride (PhPCl2) afforded novel five-member heterocycles along with other products. In the case of Ph2SiCl2, the expected product 6 was accompanied by another five-member ring 8 containing the Ph2Si-Se-Se moiety. The phospholane 13 could be oxidised to the sulfide 14 and the selenide 15, and partial hydrolysis gave the selenophosphonic acid 16 along with the bis(diselane) 18 and decomposition. The dianion 3 was converted by oxidative coupling into the bis(diselane) 18, an eight-member ring with annellated carborane moieties. Symmetric cleavage of this ring in 18 took place by oxidative addition of 18 to bis(triphenylphosphane)ethene-platinum(0) to give the (Ph3P)2Pt(II) complex 20 with the chelating 1,2-diselenido-1,2-dicarba-closo-dodecaborane(12) ligand. Oxidative addition of the five-member heterocycles containing Se-Sn-Se fragments (9, 11) to bis(triphenylphosphane)ethene-platinum(0) proceeded at low temperature by insertion of the (PPh3)2Pt fragment into one of the Sn-Se bonds (21, 22). The reaction of 11 with bis(triphenylphosphane)ethene-platinum(0) took place by oxidative addition of the P-Se bond, followed by rearrangement (25). The molecular structures of the five-member rings with annellated carborane units 4 (CPh2), 11 (SnPh2), 13 (PPh), 14 (PhP=S), 20 (Pt(PPh3)2, and of the bis(diselane) 18 were determined by X-ray analyses.The proposed solution-state structures of the new compounds followed from consistent sets of multinuclear magnetic resonance data ( 1 H, 11 B, 13 C, 29 Si, 31 P, 77 Se, 119 Sn and 195 Pt NMR).

Novel main group chemistry of the 1,2-diselenido-1,2-dicarba-closo-dodecaborane(12) dianion