Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

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−)

“…Each Cu atom has a distorted tetrahedral coordination geometry. The mean MoÁ Á ÁCu contact, Mo-l 3 -S and Cu-l 3 -S bond lengths are comparable to those found in other Mo 2 S 4 Cu 2 cubane-like clusters such as [(dtc) 2 Mo 2 (l 3 -S) 4 (CuBr) 2 ] [43] and [(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 4 (CuX) 2 ] (X=Cl, I) [40,41]. The mean MoÁ Á ÁMo contact is longer than that in [(dtc) 2 Mo 2 (l 3 -S) 4 (CuBr) 2 ], but comparable to those in [(g 5 -C 5 Me 5 ) 2 Mo 2 (l 3 -S) 4 (CuX) 2 ] (X = Cl, I).…”

“…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]. In fact, we have recently reported that treatment of a suspension of 1 in methylene dichloride with 2 equiv.…”

Synthesis of Two Heterobimetallic Cluster Isomers [(η5-C5Me5)2Mo2(μ3-S)3S(CuI)2] and [(η5-C5Me5)2Mo2(μ3-S)4(CuI)2] from trans-[(η5-C5Me5)2Mo2(μ-S)2S2] and Their trans-to-cis Isomerization, Structures, and Third-Order NLO Properties

“…The molecular structure of 3 closely resembles that of [(η 5 -C 5 Me 5 ) 2 Mo 2 (μ 3 -S) 4 (CuCl) 2 ] 7 and [(dtc) 2 Mo 2 (μ 3 -S) 4 (CuBr) 2 ] (dtc = diethyldithiocarbamate) . The mean Mo···Cu contact (2.7832(11) Å) and Cu−μ 3 -S (2.3438(14) Å) and Mo−μ 3 -S (2.2943(13) Å) bond lengths are close to those of the corresponding ones of [(η 5 -C 5 Me 5 ) 2 Mo 2 (μ 3 -S) 4 (CuCl) 2 ].…”

“…The chemistry of clusters consisting of [M 2 S 4 ] (M = Mo, W) cores and transition metals has been of considerable interest because of their rich structural chemistry − and their potential applications in the industrial hydrodesulfurization (HDS) process, simulating the active site of nitrogenase, and the hydrogenation of unsaturated bonds . In many cases, various transition metals usually were used to react with species containing [M 2 S 4 ] cores to form various [M 2 S 4 M‘ 2 ] (M‘ = Co, Ni, Fe, Cu, Ir, Rh, Pt, Pd) clusters.…”

“…In many cases, various transition metals usually were used to react with species containing [M 2 S 4 ] cores to form various [M 2 S 4 M‘ 2 ] (M‘ = Co, Ni, Fe, Cu, Ir, Rh, Pt, Pd) clusters. Among the limited copper complexes, − one intriguing example is a cubane-like cluster, [(η 5 -C 5 Me 5 ) 2 Mo 2 (μ 3 -S) 4 (CuCl) 2 ], which was prepared by refluxing a solution containing trans -[(η 5 -C 5 Me 5 ) 2 Mo 2 (μ-S) 2 S 2 ] ( 1 ) and 2 equiv of CuCl in toluene . During this reaction, the original trans structrue of 1 was converted into its cis structure in the cubane-like cluster.…”