Diselenastanna‐, ‐sila‐ and ‐carbacycles with an annelated dicarba‐ closo ‐dodecaborane(12) unit

The reactions of the 1,2‐diselenolato‐1,2‐dicarba‐ closo ‐dodecaborane(12) dianion 1 with diorganoelement(IV) dichlorides (Ph 2 CCl 2 , Me 2 SiCl 2 , Ph 2 SiCl 2 , Me 2 SnCl 2 , Ph 2 SnCl 2 ) gave novel five‐member heterocycles along with other products. The molecular structures of the five‐member rings containing CPh 2 ( 2 ) and SnPh 2 ( 9 ) moieties between the selenium atoms were determined by X‐ray analyses. In the case of the chlorosilanes, the analogous five‐member ring containing the SiPh 2 unit ( 4 ) could be identified in mixtures. The expected reaction was accompanied by rearrangement leading to formation of another five‐member ring 6 containing the Ph 2 SiSeSe moiety. Oxidative addition of the five‐member heterocycles containing tin ( 7, 9 ) to ethene‐bis(triphenylphosphane)platinum(0) gave at low temperature the bis(triphenylphosphane)platinum(II) complexes 12 and 13 , where the Pt(PPh 3 ) 2 fragment had been inserted into one of the SnSe bonds. Extensive decomposition of these complexes was observed above − 20 °C. The proposed solution‐state structures of the new compounds are supported by multinuclear magnetic resonance data ( 1 H, 11 B, 13 C, 29 Si, 31 P, 77 Se, 119 Sn and 195 Pt NMR). Copyright © 2007 John Wiley & Sons, Ltd.