Syntheses, Crystal Structures and Optical Limiting Properties of Three Novel Organometallic Tungsten‐Copper‐Sulfur Clusters: [PPh₄][(η⁵‐C₅Me₅)WS₃(CuCN)₂], [(η⁵‐C₅Me₅)WS₃Cu₂(PPh₃)(μ‐CN)]₂ and [PPh₄][{(η⁵‐C₅Me₅)WS₃Cu₂(CN)(Py)}₂(μ‐CN)]

Abstract

Reactions of [PPh4][(η5‐C5Me5)WS3] with two equivalents of CuCN in MeCN produced a novel trinuclear butterfly‐shaped cluster [PPh4][(η5‐C5Me5)WS3(CuCN)2] (1) in a 70% yield. Treatment of 1 with excess PPh3 or Py gave rise to two different hexanuclear clusters [(η5‐C5Me5)WS3Cu2(PPh3)(μ‐CN)]2 (2) and [PPh4][{(η5‐C5Me5)WS3Cu2(CN)(Py)}2(μ‐CN)] (3), respectively. Compounds 1−3 were fully characterized by spectroscopy and X‐ray crystallography. The structure of the cluster anion of 1 contains a butterfly‐like WS3Cu2 fragment in which each Cu atom is coordinated to one μ‐S atom, one μ3‐S atom, and one terminal CN group. The neutral compound 2 has a double butterfly‐shaped structure in which two WS3Cu2 fragments are interconnected by two Cu−μ‐CN−Cu bridges. The anion of 3 adopts another type of double butterfly‐shaped structure in which the two WS3Cu2 fragments are linked by a single Cu−μ‐CN−Cu bridge. Compared with C60 in terms of the optical limiting (OL) properties measured under identical conditions, 1 and 2 exhibit a relatively good OL performance, whereas the OL effect is not observed for 3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Two W/Cu/S clusters: tetraethylammonium bromidodi-μ2-sulfido-sulfido[tris(3,5-dimethylpyrazol-1-yl)borato]copper(I)tungsten(VI) and tetraethylammonium dibromido-μ3-sulfido-di-μ2-sulfido-[tris(3,5-dimethylpyrazol-1-yl)borato]dicopper(I)tungsten(VI)

“…Each Cu atom in (II) adopts a trigonal planar geometry, coordinated by one -S atom, one 3 -S atom and one terminal Br atom. The WÁ Á ÁCu distance of 2.6239 (10) Å is longer than that in complex (I), but similar to those found in other complexes containing three-coordinated Cu, such as ( Lang et al, 2004]. Because of the coordination of the S atoms to the Cu atoms, the W1-S1 bond length of 2.331 (2) Å is longer than the W1-S2 bond length of 2.2293 (18) Å , and both bonds are elongated relative to the mean W-S bond length (2.193 Å ) in the precursor (Et 4 N)[Tp*WS 3 ] (Seino et al, 2001).…”

“…Atoms W1, S1, B1, N3, N4 and C6-C10 lie on a crystallographic mirror plane. Similar butterfly-shaped (Lang et al, 2004) and ller et al, 1983). Each Cu atom in (II) adopts a trigonal planar geometry, coordinated by one -S atom, one 3 -S atom and one terminal Br atom.…”

Synthesis, crystal structures and third-order nonlinear optical properties of a new family of double incomplete cubane-like clusters [(η5-C5Me5)2Mo2(μ3-S)3SCu2X(μ-X)]2 (X=Cl−, Br−, SCN−) and cubane-like clusters [(η5-C5Me5)2Mo2(μ3-S)4(CuX)2] (X=Br−, SCN−, CN−)

“…Some of these clusters exhibited good third-order nonlinear optical (NLO) properties in solution [16,26,[30][31][32]36,37,39]. In order to expand the chemistry of Mo(W)/Cu/S clusters and screen out clusters with better NLO performances, we have became to adopt other Mo(W)/S precursors including 1 [41][42][43].…”

“…On the other hand, we have been interested in the synthesis of Mo(W)/Cu/S clusters derived from [MO 4Àn S n ] 2À and [(g 5 -C 5 Me 5 )MS 3 ] À (M = Mo, W) [13,14,[16][17][18][19][20][21][22][23][24][25][26][27][30][31][32]39]. Some of these clusters exhibited good third-order nonlinear optical (NLO) properties in solution [16,26,[30][31][32]36,37,39].…”

“…The reactions of thiomolybdates and thiotungstates [MO 4Àn S n ] 2À and [(g 5 -C 5 Me 5 )MS 3 ] À (M = Mo, W) with copper(I) salts have been extensively investigated due to their rich chemistry , and their relations to biological systems [1,5,6,28,29], and electro/photonic materials [11,15,16,24,26,[30][31][32][33][34][35][36][37][38][39]. However, only a few reactions are involved in the utilization of the disulfido-bridged dimolybdenum clusters [Cp 0 2 Mo 2 S 4 ] (Cp 0 = g 5 -C 5 H 5 , g 5 -C 5 H 4 Me or g 5 -C 5 Me 5 ) [40,41].…”