Selenium and tellurium derivatives of a monocarbon platinacarbaborane complex

Stewart A. Batten, John C. Jeffery, Leigh H. Rees, Martin D. Rudd, F. Gordon A. Stone

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The reaction between Na[Pt(PEt3)25-7-CB10H 11)] 1 and PhSeCl in thf (tetrahydrofuran) afforded a mixture containing the isomeric species [Pt(SePh)(PEt3)(η5-n-SePh-7-CB10H 10)] (n = 8 2a or 9 2b) and the compound [Pt(SePh)(PEt3){η5-8-O(CH2) 4Cl-7-CB10H10}] 3. The molecular structures of complexes 2a and 3 were established by X-ray crystallography. Both molecules have Pt(SePh)(PEt3) groups with the platinum atoms pentahapto co-ordinated by nido-7-CB10 cage frameworks. In 2a the cage substituted SePh group is attached to the boron atom in the α site with respect to the carbon in the CBBBB ring ligating the platinum and this is true also of the O(CH2)4Cl substituent in 3. The isomers 2 are also formed when PhSeSePh is used instead of PhSeCl. Treatment of the salt 1 with PhTeI in thf yielded a mixture of [Pt(PEt3)25-9-Te(Ph)CH 2Cl-7-CB10H10}] 4 and [Pt2(TePh)(μ-TePh)2(PEt3) 25-2-CB10H11)] 5. Single-crystal X-ray diffraction studies were employed to establish the formulations and molecular structures of both molecules. Compound 4 is a charge-compensated platinacarbaborane with a Pt(PEt3)2 group and with the mido-7-CB10 framework carrying a Te(Ph)CH2Cl moiety at the boron vertex situated in the β site with respect to the carbon in the CBBBB ring ligating the platinum. Complex 5 is a diplatinum species in which Pt(TePh)(PEt3) and Pt(PEt3)(η5-2-CB10H11) units are bridged by two TePh groups. The X-ray study revealed that in forming compound 5 from the reagent 1 the nido-7-CB10H11 cage system has undergone an unusual polytopal rearrangement to a nido-2-CB10H11 framework.

Original languageEnglish
Pages (from-to)2839-2847
Number of pages9
JournalJournal of the Chemical Society - Dalton Transactions
Issue number17
Publication statusPublished - 1998
Externally publishedYes

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