Macrocycles Incorporating Sulfur and nido -Carborane Cages: Reactivity toward Nickel(II) and Palladium(II). Molecular Structures of Pd{7,8-μ-(S(CH<inf>2</inf>CH<inf>2</inf>OCH<inf>2</inf>CH<inf>2</inf>OCH<inf>2</inf>CH<inf>2</inf>OCH<inf>2</inf>CH<inf>2</inf>)S)C<inf>2</inf>B<inf>9</inf>H<inf>10</inf>}<inf>2</inf> and Pd{P(C<inf>6</inf>H<inf>5</inf>)<inf>3</inf>}Cl{7,8-M-(SCH<inf>2</inf>CH<inf>2</inf>S)C<inf>2</inf>B<inf>9</inf>H<inf>10</inf>}

Francesc Teixidor, Jaume Casabó, Clara Vinas, Eustaquio Sanchez, Lluis Escriche, Raikko Kivekäs

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Abstract

The reactions of exo-dithio-7,8-dicarba-nido-undecaborate derivatives with Ni(II) and Pd(II) chlorides and phosphine chloride complexes are presented and discussed. Three different stoichiometries have been observed, [MLC12]-, [M2L2Cl2], and [ML2]. The capacity of these ligands to act as tricoordinating agents through the two sulfur atoms and a B(3)-H→M bond is introduced and discussed. A regularity in the value of the dihedral angle ω (planes defined by S-M-S and S-Cc-Cc-S) and the length of the exo-cluster chain has been observed. The shorter the exo-cluster chain is, the smaller the ω angle. The molecular structures of Pd{7,8-μ-(S(CH2CH2OCH2CH2OCH2CH2OCH2CH2)S)C2B, H10}2 and Pd{P(C6H5)3}Cl(7,8-μ-(SCH2CH2S)C2B9H10} have been determined. The former crystallizes in space group P21/c with 2 formula units per cell. The cell dimensions are a = 8.140 (2) Å, b = 20.083 (8) Å, c = 11.953 (3) Å, and β = 104.09 (2)°. The latter orystallizes in space group P21/n with 4 formula units per cell. The cell dimensions are a = 13.424 (2) Å, b = 10.315 (2) Å, c = 20.008 (4) Å, and β = 90.83 (1)°. © 1991, American Chemical Society. All rights reserved.
Original languageEnglish
Pages (from-to)3053-3058
JournalInorganic Chemistry
Volume30
Issue number15
DOIs
Publication statusPublished - 1 Jul 1991

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