Organotransition-metal Metallacarboranes 13

Alternative Title

Fulvalene- and polyarene-transition metal-carborane complexes as building blocks for multilevel arrays. Stepwise synthesis and structural characterization of polymetallic linked sandwiches

Abstract

The designed synthesis and structural elucidation of a series of linked double-decker and triple-decker arene-metal-carborane complexes, in which the sandwich moieties are linked either directly or via bridging phenylene or biphenylene groups, are reported. The reaction of fulvalenide dianion [(C5H4)2 2-] with CoCl2 and the Et2C2B4H5 - ion generated [(Et2C2B4H4)Co(C5H 4)]2 (1), the first known fulvalene-metal-carborane sandwich species, as air-stable orange crystals. “Double-decapitation” (removal of the apex BH units) of 1 gave yellow air-stable [(Et2C2B3H5)Co(C5H 4)]2 (3). The interaction of the 1,4-bis(tetramethylcyclopentadienyl)phenylene dianion [Me4C5-C6H4-C5Me 4]2- with CoCl2 and the carborane ion produced orange [(Et2C2B4H4)Co(C5Me 4)]2C6H4 (4), which on double-decapitation gave yellow [(Et2C2B3H5)Co(C5Me 4)]2C6H4 (6), both compounds isolated as air-stable crystals. Similar treatment of the [Me4C5-(C6H4)2-C 5Me4]2- dianion gave orange crystals of [(Et2C2B4H4)Co(C5Me 4)]2(C6H4)2 (7), which was decapitated to generate yellow [(Et2C2B3H5)Co(C5Me 4)]2(C6H4)2 (9); again, both species are air-stable. Linked triple-decker complexes (the first examples of this genre) were prepared via a different approach, involving reactions of [Me4C5-(C6H4)n-C 5Me4]2- anions with CoCl2 followed by (η6-MeC6H4CHMe2)Ru(Et 2C2B3H4)-, which gave emerald green air-stable [(η6-MeC6H4CHMe2)Ru(Et 2C2B3H3)Co(η5-Me 4C5)]2(C6H4)n (10, n = 1; 11, n = 2). A fulvalene-bridged bis(triple-decker) complex, emerald air-stable crystalline [(η6-MeC6H4CHMe2)Ru(Et 2C2B3H3)Co(η5-C 5H4)]2 (12), was prepared via the reaction of fulvalenide dianion with the (η6-MeC6H4CHMe2)Ru(Et 2C2B3H4)- anion and CoCl2. The complexes were structurally characterized from their 11B and 1H NMR, IR, UV-visible, and mass spectra, supported by X-ray crystallographic studies on 1, 6, and 10. Crystal data for 1: mol wt 504.87; space group Pbca; Z = 4; a = 6.764 (3), b = 13.135 (4), c = 29.22 (2) Å; V= 2596 (3) Å3; R = 0.037 for 1547 reflections having Fo 2 > 3σ(Fo 2). Crystal data for 6: mol wt 673.58; space group P21/c; Z = 2; a = 14.702 (6), b = 8.746 (2), c = 15.003 (3) Å; β = 103.35 (3)°; V = 1877 (2) Å3; R = 0.082 for 2098 reflections having Fo 2 > 3σ(Fo 2). Crystal data for 10: mol wt 1310.0; space group P1; Z = 1; a = 11.094 (3), b = 12.062 (4), c = 12.823 (3) Å; α = 78.00 (3), β = 74.77 (3), γ = 69.78 (2)°; V = 1541 (2) Å3; R = 0.056 for 3842 reflections having Fo 2 > 3σ(Fo 2). © 1989 American Chemical Society.

Department(s)

Chemistry

International Standard Serial Number (ISSN)

0002-7863

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 1989 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Jun 1989

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