Cubane‐Type [Mo₃S₄M] Clusters with First‐Row Groups 4–10 Transition‐Metal Halides Supported by C₅Me₅ Ligands on Molybdenum

Abstract

A synthetic protocol was developed for a series of cubane-type [Mo S M] clusters that incorporate halides of first-row transition metals (M) from Groups 4-10. This protocol is based on the anionic cluster platform [Cp* Mo S ] ([1] ; Cp*=η -C Me ), which crystallizes when K(18-crown-6) is used as the counter cation. Treatment of in situ-generated [1] with such transition-metal halides led to the formation of [Mo S M] clusters, in which the M/halide ratio gradually changes from 1:2 to 1:1.5 and to 1:1, when moving from early to late transition metals. This trend suggests a tendency for early transition metals to tolerate higher oxidation states and adopt larger ionic radii relative to late transition metals. The properties of the [Mo S Fe] cluster 6 a were investigated in detail by using Fe Mössbauer spectroscopy and computational methods.

Synthesis, Characterization, and Catalytic Activity of a Cubic [Mo3S4Pd] Cluster Bearing Bulky Cyclopentadienyl Ligands

“…A [Mo 3 S 4 Pd] cluster Mo 3 Pd was synthesized by the Pd II ion insertion reaction into an in-situ generated anionic [Mo 3 S 4 ] cluster ([Cp SiEt3 3 Mo 3 S 4 ] À , Mo 3 À ) (Figure 1). A neutral [Mo 3 S 4 ] cluster ([Cp SiEt3 3 Mo 3 S 4 ], Mo 3 ) prepared using the literature procedure [35,36] was reduced by potassium graphite (KC 8 , 1.2 equiv. to Mo 3 ) in THF to give Mo 3 À .…”

“…General Procedures: All reactions were carried out under an atmosphere of N 2 using either Schlenk-line or glovebox techniques. Tetrahydrofuran (THF), hexane, and acetonitrile (MeCN) were purified by passing over columns of activated alumina, and a supported copper catalyst supplied by Hansen & Co. Ltd. [(C 5 Me 4 SiEt 3 ) 3 Mo 3 S 4 ] (Mo 3 ), [35,36] PdCl 2 (cod) (cod = 1,5cyclooctadiene), [51] and KC 8 [52] were synthesized according to the reported procedure. Tetrabutylammonium hexafluorophosphate (TBAPF 6 ) was recrystallized from absolute THF.…”

“…[34] We have also reported the synthesis of [Mo 3 S 4 M] cubes and their reactivity in a relevant manner. [35][36][37] The precursor of our [Mo 3 S 4 M] cubes is cyclopentadienyl (C 5 Me 4 SiEt 3 , Cp SiEt3 )-supported [Mo 3 S 4 ] platform, of which three μ 2 -sulfides can uptake and hold one M atom. Steric protection around M imposed by the substituents of Cp SiEt3 ligands is a unique feature of our platform and prevents undesirable decomposition or aggregation of the resultant [Mo 3 S 4 M] cubes.…”

Structure, reactivity, and spectroscopy of nitrogenase-related synthetic and biological clusters

“…88 To synthesize the heterometallic cluster 13). 126 Although the afforded heterometallic clusters do not capture the properties of FeMo-cofactor, it serves as a useful tool to broaden the scope of the synthetic heterometallic clusters.…”

Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}

“…The trinuclear cluster complexes with the {M 3 S 4 } (M = Mo, W) core are able to incorporate a range of transition metals in low oxidation state (from 0 to +2), affording heterometallic cubane-type derivatives {M 3 M S 4 }, where M = Cu, Ni, Pd, Pt, etc. [11,[30][31][32][33][34][35].…”