Protonation of the 1,1-dithiolene ligands in the [Cu8(L)6]4- cubanes (L=[S2C=C(COOR)2]2-) and synthesis of the [Cu8(L)6-n(H-L)n]-(4-n) clusters. Synthesis and structural characterization of the [Cu10(H-L)6(L)2] decanuclear cluster

D Coucouvanis; D Swenson; N. C Baenziger; R Pedelty; M. L Caffery; S Kanodia

doi:10.1021/ic00313a028

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Protonation of the 1,1-dithiolene ligands in the [Cu8(L)6]4- cubanes (L=[S2C=C(COOR)2]2-) and synthesis of the [Cu8(L)6-n(H-L)n]-(4-n) clusters. Synthesis and structural characterization of the [Cu10(H-L)6(L)2] decanuclear cluster

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Protonation of the 1,1-dithiolene ligands in the [Cu8(L)6]4- cubanes (L=[S2C=C(COOR)2]2-) and synthesis of the [Cu8(L)6-n(H-L)n]-(4-n) clusters. Synthesis and structural characterization of the [Cu10(H-L)6(L)2] decanuclear cluster

D Coucouvanis, D Swenson, N. C Baenziger, R Pedelty, M. L Caffery and S Kanodia

Inorganic chemistry, Vol.28(14), pp.2829-2836

07/01/1989

DOI: 10.1021/ic00313a028

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Abstract

Addition of 1, 2, or 3 equiv of acid to CH3CN solutions of the K4Cu8(R2DED)6cubane cluster complexes (R2DED = [S2C= C(COOR)2]2-; R = Et (I), t-Bu (II)) by using standarized HC104/CH3CN solutions results in the formation of the protonated complexes [Cu8(L)6-n(H-L)n]-4-n(L = Et2DED, n = 1, 2, 3; L = t-Bu2DED, n = 1, 2) that were isolated as crystalline tetraarylphosphonium or tetraalkylammonium salts. The protonated clusters can be titrated with standard base to give back the “parent” cubanes in quantitative yields. The cubane structure of the [Cu8(L)5(H-L)]3-(L = t-Bu2DED) cluster has been established unequivocally by13C NMR spectroscopy. Upon addition of 4 equiv of acid to K4Cu8(f-Bu2DED)6, a red Cu(I) cluster of stoichiometry [Cu10(H-L)6(L)2] (L = t-Bu2DED) forms and can be isolated in crystalline form (III). Neutral complex III crystallizes in the triclinic space group P1 with one molecule per unit cell. The cell dimensions are a = 14.435 (3) A, b = 16.979 (3) A, c = 14.843 (3) A, a = 98.16 (4)°, β = 108.90 (2)°, ϒ= 85.42 (4)°. Intensity data were collected with a four-circle computer-controlled diffractometer using the θ–2θ scan technique. Refinement by full-matrix least-squares techniques of 374 parameters on 4284 data gave a final R value of 0.067. The copper framework in III consists of two Cu4subunits. of the four ligands surrounding each of the Cu4subunits, three are protonated at the ethylenic carbon adjacent to the CS2unit (“methine” carbon) and can be considered dithio acid monoanions (H-t-Bu2DED)_. The fourth ligand is a 1,1-efhylenedithiolate dianion, (t-Bu2DED)2-. The latter connects the Cu4fragment to the bridging copper atom by coordination via oxygen and sulfur atoms. A third coordination site on the bridging copper is occupied by a dithio acid sulfur on the adjacent Cu4fragment. The coordination geometry about each of the copper atoms in the structure is distorted trigonal and nearly planar. Ranges of selected structural parameters are as follows: Cu-S, 2.230 (3)-2.322 (3) A; Cu-Cu, 2.656 (2)—3.056 (2) A; Cu-O, 1.898 (8) A; S-Cu-S, 106.0 (1)-131.8 (1)°; Cu-S-C, 98.5 (4)-l 10.0 (4)°.

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Title: Subtitle: Protonation of the 1,1-dithiolene ligands in the [Cu8(L)6]4- cubanes (L=[S2C=C(COOR)2]2-) and synthesis of the [Cu8(L)6-n(H-L)n]-(4-n) clusters. Synthesis and structural characterization of the [Cu10(H-L)6(L)2] decanuclear cluster
Creators: D Coucouvanis - Univ. Michigan, dep. chemistry, Ann Arbor MI 48109, United States
D Swenson - Univ. Michigan, dep. chemistry, Ann Arbor MI 48109, United States
N. C Baenziger - Univ. Michigan, dep. chemistry, Ann Arbor MI 48109, United States
R Pedelty - Univ. Michigan, dep. chemistry, Ann Arbor MI 48109, United States
M. L Caffery - Univ. Michigan, dep. chemistry, Ann Arbor MI 48109, United States
S Kanodia - Univ. Michigan, dep. chemistry, Ann Arbor MI 48109, United States
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.28(14), pp.2829-2836
Publisher: American Chemical Society
DOI: 10.1021/ic00313a028
ISSN: 0020-1669
eISSN: 1520-510X
Language: English
Date published: 07/01/1989
Academic Unit: Chemistry
Record Identifier: 9984622046002771

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