Solvothermal Synthesis of a New Mixed-Metal Polysulfide Cluster, [Me₄N]₃[MoS₄Cu₃(S₅)₂]

Abstract

A new mixed-metal polysulfide complex, [Me4N]3[MoS4Cu3(S5)2], has been synthesized and structurally characterized. The tetranuclear trianion has C 2 symmetry, and the boat−chair eight-membered metallacyclic S5Cu2S rings interact through S···S weak interaction to form infinite chains along the [201] direction.

Sulfido-Bridged Dinuclear Molybdenum−Copper Complexes Related to the Active Site of CO Dehydrogenase: [(dithiolate)Mo(O)S2Cu(SAr)]2- (dithiolate = 1,2-S2C6H4, 1,2-S2C6H2-3,6-Cl2, 1,2-S2C2H4)

“…Müller et al. have demonstrated that the terminal sulfide ligands in MoS 4 2- readily bind to CuCN to afford both dinuclear [MoS 4 (CuCN)] 2- and trinuclear [MoS 4 (CuCN) 2 ] 2- complexes 6a. However, the reaction of [MoO 2 S 2 ] 2- with CuCN afforded exclusively the dinuclear complex 1 , since the terminal oxo ligands have lower affinity toward late transition metals because of their hard character.…”

“…We have chosen the latter strategy since molybdenum sulfide complexes with one dithiolene ligand are unknown. 4a-c A logical starting point for the construction of the dinuclear Mo−Cu unit is to use simple thiomolybdates, [MoO 4 - n S n ] 2- ( n = 1−4), since they have remarkable affinity toward transition metals. Thus, the reaction with copper complexes readily takes place to form various types of multinuclear Mo−Cu complexes, , including dinuclear [S 2 MoS 2 Cu(CN)] 2- , 6a, [S 2 MoS 2 Cu(SAr)] 2- , and [OSMoS 2 Cu(CN)] 2- …”

Synthesis and Crystal Structure of the New Quaternary Polysulfide Na8Cu4Nb2S21 Containing S2-, S32-, and S52- Anions in Different Bridging Modes

“…The average S−S distance within the S 5 2- polyanion is 2.071 Å with a bonding pattern “long−short−medium−medium” (see Table ). Depending on the actual bonding mode, other sequences were reported. − …”

“…In KAuS 5 the two terminal S atoms connect two Au centers leading to the formation of 1D chains . In [Me 4 N] 3 [MoS 4 Cu 3 (S 5 ) 2 ] the two S 5 2- anions bridge across a pair of Cu atoms to form a S 5 Cu 2 S metallacycle . A bidentate behavior was reported for (PPh 4 ) 2 [Te(S 5 ) 2 ] .…”

(Et4N)2[(Mo2O2Se6)0.20(Mo2O2Se7)0.18(Mo2O2Se8)0.62], a New Dimeric Molybdenum Polyselenide Containing a [Mo2O2(μ-Se)2] Core

“…Development in the chemistry of molybdenum sulfides started with the initial reports on the synthesis and structure of [(S 2 ) 2 Mo(μ-S 2 )] 2 2- 21a and [Mo 3 S 13 ] 2- 21b by Müller et al Numerous complexes containing the dimeric [M 2 X 2 (μ-E) 2 ] core are now generally prepared by the following synthetic methods: (1) reaction of [MS 4 ] 2- (M = Mo, W) with sulfur or organic polysulfides, ,9b,,17a in which an externally induced internal redox pathway has been proposed as the mechanism for the formation of dimeric complexes; (2) an intramolecular redox process based on the acidification or heating of the tetrathiomolybdates/tetrathiotungstates/tetraselenidotungstates; 11a,12e,h,19b and (3) interconversion of various isomers of [M 2 E n ] 2- (M = Mo, W; E = S, Se; n = 6−12) by addition or removal of sulfur or selenium. 2b,8a,9a,,,17a,19c Recently we became interested in the use of the hydro(solvo)thermal technique for the preparation of transition metal polychalcogenides . In this paper we report the solvothermal synthesis and structure of the new compound (Et 4 N) 2 [(Mo 2 O 2 Se 6 ) 0.20 (Mo 2 O 2 Se 7 ) 0.18 (Mo 2 O 2 Se 8 ) 0.62 ], in which the major component ion [Mo 2 O 2 (μ-Se) 2 (Se 2 )(Se 4 )] 2- is found for the first time.…”