Formation of new organometallic W/Cu/S clusters from reactions of [{(η5-C5Me5)WS3}3Cu7(MeCN)9](PF6)4 with donor ligands. Crystal structures and optical limiting properties of [(η5-C5Me5)WS3Cu3(Py)6](PF6)2, [(η5-C5Me5)WS3Cu3Br(PPh3)3](PF6), and [(η5-C5Me5)WS3Cu4(Py)Cl(dppm)2](PF6)2

Yu, Hong; Zhang, Wen Hua; Ren, Zhoupeng; Chen, Jinxiang; Wang, Chunlan; Liu, Jianping; Elim, Hendry Izaac; Ji, Wei

doi:10.1016/j.jorganchem.2005.06.003

Cited by 18 publications

(10 citation statements)

References 47 publications

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“…There is a 3-fold axis going through H1, B1, W1, and Br1. The resulting [W(μ 3 -S) 3 Cu 3 (μ 3 -Br)] cube closely resembles those observed in [Cp*W(μ 3 -S) 3 Cu 3 (μ 3 -Br)(PPh 3 ) 3 ](PF 6 ) and [WS(μ 3 -S) 3 Cu 3 (μ 3 -Br)(PPh 3 ) 3 ]·H 2 O . As shown in Table , the mean W1···Cu contact (2.6390(13) Å) in 1 is almost identical to that of its chloride analogue (2.6404(18) Å), but slightly shorter than those found in the three-coordinated Cu clusters such as 2 (2.6679(13) Å) and [PPh 4 ][Cp*W(μ 3 -S) 3 (CuBr) 3 ] (2.661(1) Å) .…”

Section: Resultssupporting

confidence: 75%

“…However, mixing 1 and NH 4 PF 6 (molar ratio = 1:3) in excess pyridine followed by a standard workup gave rise to the cationic cluster 2 in 45% yield (Scheme ). The idea for introducing the large anion salt NH 4 PF 6 into this reaction came from the formation of dicationic cluster [Cp*W(μ 3 -S) 3 Cu 3 (py) 6 ](PF 6 ) 2 from reactions of [{Cp*W(μ 3 -S) 3 } 3 Cu 7 (MeCN) 9 ](PF 6 ) 4 with excess pyridine . The different outcomes for the above two reactions may be ascribed to the fact that the Tp* group is more bulky than the Cp* group and thus blocks the second py ligand coordinated at each Cu(I) site of 2 .…”

Section: Resultsmentioning

confidence: 99%

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Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et₄N][Tp*W(μ₃-S)₃(CuBr)₃] and Various Nitrogen Donor Ligands

Wei

Cheng

et al. 2009

Inorg. Chem.

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Assembly of a family of monomeric, dimeric, and polymeric W/Cu/S clusters from a precursor cluster [Et(4)N][Tp*W(mu(3)-S)(3)(CuBr)(3)] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) and various N-donor ligands was reported. The treatment of 1 with pyridine (py) or aniline (ani) in the presence of NH(4)PF(6) afforded a cationic cluster [Tp*W(mu(3)-S)(3)Cu(3)(py)(3)(mu(3)-Br)](PF(6)) (2) and a neutral cluster [{Tp*W(mu(3)-S)(3)(CuBr)(3)}(mu(6)-Br){Tp*W(mu(3)-S)(3)Cu(3)(ani)(3)}] x 4 ani x 0.5 Et(2)O (3 x 4 ani x 0.5 Et(2)O). On the other hand, the treatment of 1 with excess 4,4'-bipyridine (4,4'-bipy) or 1,2-bis(4-pyridyl)ethylene (bpee) followed by the addition of NH(4)PF(6) led to the formation of a polymeric cluster {[Tp*W(mu(3)-S)(3)Cu(3)(4,4'-bipy)(3)(mu(3)-Br)](PF(6)) x H(2)O}(n) (4) and a neutral cluster [{Tp*W(mu(3)-S)(3)Cu(3)Br(2)}(2)(bpee)] x 0.5 CH(2)Cl(2) (5 x 0.5 CH(2)Cl(2)). Meanwhile, analogous reactions of 1 with excess 1,2-bis(4-pyridyl)ethane (bpe) or 1,3-bis(4-pyridyl)propane (bpp) in DMF under the presence of NH(4)PF(6) resulted in the formation of two polymeric clusters {[{Tp*W(mu(3)-S)(3)Cu(3)(mu(3)-Br)}(2)(bpe)(3)](PF(6))(2) x MeCN}(n) (6) and {[Tp*W(mu(3)-S)(3)Cu(3)Br(mu(3)-Br)(bpp)] x DMF}(n) (7). Compounds 1-7 were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, electrospray ionization mass spectra, and X-ray crystallography. The anion of 1 has an incomplete cubanelike [Tp*W(mu(3)-S)(3)(CuBr)(3)] structure, while the cation of 2 has a cubanelike [Tp*W(mu(3)-S)(3)Cu(3)(mu(3)-Br)] structure. Compound 3 may be viewed as having a corner-shared double cubanelike structure that consists of one [Tp*W(mu(3)-S)(3)Cu(3)(ani)(3)](2+) dication and one [Tp*W(mu(3)-S)(3)(CuBr)(3)](-) anion linked by a mu(6)-Br bridge. For 4, each [Tp*W(mu(3)-S)(3)Cu(3)(mu(3)-Br)] unit works as a pyramidal three-connecting node to connect its equivalent ones via three 4,4'-bipy bridges to yield a 2D (6,3) cationic network. Compound 5 has a dimeric structure in which two incomplete cubanelike [Tp*W(mu(3)-S)(3)Cu(3)Br(2)] cores are bridged with one bpee ligand. For 6, each dimeric [{Tp*W(mu(3)-S)(3)Cu(3)(mu(3)-Br)}(2)(bpe)(2)] unit is interconnected via a pair of bpe bridges to form a 1D zigzag cationic chain. Compound 7 has a 1D spiral chain in which each [Tp*W(mu(3)-S)(3)Cu(3)Br(mu(3)-Br)] core is interlinked by a couple of bpp bridges. The formation of 2-7 from the precursor cluster 1 through various N-donor ligands offers a new way to the design and assembly of the W/Cu/S clusters with interesting molecular and supramolecular arrays.

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Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 99%

Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et₄N][Tp*W(μ₃-S)₃(CuBr)₃] and Various Nitrogen Donor Ligands

Wei

Cheng

et al. 2009

Inorg. Chem.

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“…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].…”

Section: Introductionmentioning

confidence: 99%

“…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].…”

Section: Introductionmentioning

confidence: 99%

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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−)

Ren

et al. 2007

Journal of Organometallic Chemistry

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Reactions of [Et₄N][Tp*W(μ₃‐S)(μ‐S)₂(CuSCN)₂] with Nitrogen Donor Ligands: Syntheses, Structures, and Third‐Order Nonlinear Optical Properties

Wei

Ren

et al. 2009

Eur J Inorg Chem

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Reactions of the preformed cluster [Et4N][Tp*W(μ3‐S)(μ‐S)2(CuSCN)2] (1) with pyridine (py), 4,4′‐bipyridine (4,4′‐bipy), or 1,3‐bis(4‐pyridyl)propane (bpp) led to the formation of three neutral [Tp*W(μ3‐S)(μ‐S)2Cu2]‐based compounds [Tp*W(μ3‐S)(μ‐S)2Cu2(SCN)(py)2] (2), [{Tp*W(μ3‐S)(μ‐S)2Cu2(SCN)}2(4,4′‐bipy)]·3.5H2O (3·3.5H2O), and [Tp*W(μ3‐S)(μ‐S)2Cu2(SCN)(bpp)]2 (4), respectively. Compounds 2–4 were characterized by elemental analysis, IR spectra, UV/Vis spectra, 1H NMR, and X‐ray analysis. There are two linkage isomers [Tp*W(μ3‐S)(μ‐S)2Cu2(SCN)(py)2] and [Tp*W(μ3‐S)(μ‐S)2Cu2(NCS)(py)2], each of which has its own enantiomeric pair in the crystal of 2. Compound 3 has a double butterfly‐shaped structure in which two [Tp*W(μ3‐S)(μ‐S)2Cu2(SCN)] fragments are linked with a single 4,4′‐bipy bridge. For 4, the two butterfly‐shaped [Tp*W(μ3‐S)(μ‐S)2Cu2(SCN)] fragments are interconnected by a pair of bpp bridges. The third‐order nonlinear optical (NLO) performances of 2–4 in DMF were also investigated by Z‐scan techniques.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

show abstract

Formation of new organometallic W/Cu/S clusters from reactions of [{(η5-C5Me5)WS3}3Cu7(MeCN)9](PF6)4 with donor ligands. Crystal structures and optical limiting properties of [(η5-C5Me5)WS3Cu3(Py)6](PF6)2, [(η5-C5Me5)WS3Cu3Br(PPh3)3](PF6), and [(η5-C5Me5)WS3Cu4(Py)Cl(dppm)2](PF6)2

Cited by 18 publications

References 47 publications

Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et₄N][Tp*W(μ₃-S)₃(CuBr)₃] and Various Nitrogen Donor Ligands

Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et₄N][Tp*W(μ₃-S)₃(CuBr)₃] and Various Nitrogen Donor Ligands

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−)

Reactions of [Et₄N][Tp*W(μ₃‐S)(μ‐S)₂(CuSCN)₂] with Nitrogen Donor Ligands: Syntheses, Structures, and Third‐Order Nonlinear Optical Properties

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Formation of new organometallic W/Cu/S clusters from reactions of [{(η5-C5Me5)WS3}3Cu7(MeCN)9](PF6)4 with donor ligands. Crystal structures and optical limiting properties of [(η5-C5Me5)WS3Cu3(Py)6](PF6)2, [(η5-C5Me5)WS3Cu3Br(PPh3)3](PF6), and [(η5-C5Me5)WS3Cu4(Py)Cl(dppm)2](PF6)2

Cited by 18 publications

References 47 publications

Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et4N][Tp*W(μ3-S)3(CuBr)3] and Various Nitrogen Donor Ligands

Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et4N][Tp*W(μ3-S)3(CuBr)3] and Various Nitrogen Donor Ligands

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−)

Reactions of [Et4N][Tp*W(μ3‐S)(μ‐S)2­(CuSCN)2] with Nitrogen Donor Ligands: Syntheses, Structures, and Third‐Order Nonlinear Optical Properties

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Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et₄N][Tp*W(μ₃-S)₃(CuBr)₃] and Various Nitrogen Donor Ligands

Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et₄N][Tp*W(μ₃-S)₃(CuBr)₃] and Various Nitrogen Donor Ligands

Reactions of [Et₄N][Tp*W(μ₃‐S)(μ‐S)₂(CuSCN)₂] with Nitrogen Donor Ligands: Syntheses, Structures, and Third‐Order Nonlinear Optical Properties