Synthesis and Structural Characterization of a Halide-Free Rhombohedral Silver-Alkynyl Cage Complex [Ag14(C2tBu)12][BF4]2 Omar

Thesis

Howard[b], Omar M. Abu-Salah,*[a] Mohammed H. Ja’far,[a] Abdel Razzak Al-Ohaly,[a] Khalid A. Al-Farhan,[a] Hamda S. Al-Enzi,[a] Oleg V. Dolomanov,[b] and Judith A. K. . 2006

• Publication Work Type: paper
• Publication Online URL: Eur. J. Inorg. Chem. 2006, 2353–2356

Publication Abstract

The novel cationic complex [Ag14(C2tBu)12]2+ has been synthesized
by four reactions: reaction of [Ag(C2tBu)]n and
AgBF4 in acetone in a 6:1 mole ratio, that of HCCtBu and
AgBF4 in water in the absence of a base, treatment of
[AgC2tBu]n with HBF4 in acetone or that of {[Ag3(C2tBu)2]-
Introduction
Since the pioneering work of Nast[1] on acetylide complexes,
dramatic developments in the field, parallel to the
advances in organometallic chemistry, have been accomplished.
The versatile mode of bonding of the alkynyl
ligand resulted in numerous polynuclear alkynyl complexes.[
2,3] Different aspects of the subject have been reviewed
extensively.[2,4] Luminescence properties, particularly
of mixed-metal platinum(ii)-copper(i) and -silver(i) alkynyl
complexes have been studied widely.[5] In the field of
pure coinage metal alkynyls, new aspects of organometallic
chemistry emerged when bis(phenylethynyl) metallates
[M(C2Ph)2]– (M = Cu, Ag, Au) were treated with metal
phenylacetylide polymers [M(C2Ph)]n (M = Cu, Ag, Au).
Consecutive steps of ethynylation and condensation of
the formed anionic and cationic moieties resulted in the
formation of homonuclear [Ag5(C2Ph)6]– and heteronuclear
[Au2Cu(C2Ph)4]–, [Au3
M2(C2Ph)6]– (M = Cu, Ag),
[Ag6Cu7(C2Ph)14]– and [AuAg6Cu6(C2Ph)14]– complexes.[6]
Extension of ethynylation reactions to neutral complexes
resulted in the complexes [Au2Ag2(C2Ph)4(PPh3)2],
[Ag2Cu2(C2Ph)4(PPh3)4], [AuAg(C2Ph)2]n, [AuCu(C2Ph)2]n
and [AgCu(C2Ph)2]n.[6i,7] Silver cages of various structures
encapsulating the dianion C2
2–, which is isoelectronic with
CN–, have been reported.[8] Recently anion-templated,
rhombohedral silver-alkynyl cages [Ag14(C2tBu)12X]+ (X =
[a] Chemistry Department, College of Science, King Saud University,
P. O. Box 2455, Riyadh 11451, Saudi Arabia
Fax: + 966-1-4675992,
E-mail: [e-mail]
[b] Chemistry Department, Durham University,
South Road, Durham DH1 3LE, UK
E-mail: [e-mail]
Eur. J. Inorg. Chem. 2006, 2353–2356 © 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2353
[BF4]}n with [Ag(C2tBu)]n in a 1:4 mole ratio. Single-crystal
X-ray studies showed it to be a hexacapped cube of silver(I)
atoms, with twelve η1, μ3-C2tBu ligands.