2009
DOI: 10.1021/ic901243m
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Sequential Construction of One, Two, or Three Dithiolene Ligands from Alkynes and Sulfur in Dinuclear Cyclopentadienyl Molybdenum Complexes

Abstract: This paper describes the sequential assembly of up to three dithiolene ligands from alkynes and elemental sulfur at a dimetal center. The dimolybdenum mu-alkyne complexes [Mo(2)(mu-R(1)C[triple bond]CR(2))(CO)(4)Cp(2)] (1a-c; Cp = eta-C(5)H(5), R(1) = R(2) = H, CO(2)Me; R(1) = H, R(2) = CO(2)Me) undergo oxidative decarbonylation on reaction with elemental sulfur in refluxing toluene to give good to excellent yields of the terminal dithiolene complexes [Mo(2)(S)(mu-S)(2)(SCR(1)=CR(2)S)Cp(2)] (2a-c). Further rea… Show more

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Cited by 5 publications
(9 citation statements)
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“…In the studied complexes, the overall geometry around the metal centre is closely similar to those reported for analogous Mo and W dioxo complexes with aminobisphenolates. (7) 73.88 (8) typical for molecular tungsten sulphido complexes used as structural analogues of the oxidized sites in the xanthine oxidoreductase enzyme family. In all these compounds, the WvS bond lengths (2.16-2.17 Å), are Scheme 1 Syntheses of disulphido complexes.…”
Section: Synthesismentioning
confidence: 99%
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“…In the studied complexes, the overall geometry around the metal centre is closely similar to those reported for analogous Mo and W dioxo complexes with aminobisphenolates. (7) 73.88 (8) typical for molecular tungsten sulphido complexes used as structural analogues of the oxidized sites in the xanthine oxidoreductase enzyme family. In all these compounds, the WvS bond lengths (2.16-2.17 Å), are Scheme 1 Syntheses of disulphido complexes.…”
Section: Synthesismentioning
confidence: 99%
“…an unsaturated and potentially non-innocent bidentate dianionic ligand where two donor atoms are both sulphur. [5][6][7][8] In the latter reactions, the formation of the five-membered ring structure is associated with a formally twoelectron reduction of the metal centre. 3,4 Although there are several ways to prepare metal complexes with dithiolene ligands, there are no routine procedures for tungsten dithiolenes.…”
Section: Introductionmentioning
confidence: 99%
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“…4 Given the scientific significance of dithiolene complexes, it is important to develop new methods for their synthesis and to produce new examples of these systems. 5 Dithiolene ligands have been synthesised by several methods, including the combination of an alkyne with sulfur in a variety of its chemical forms. 5,6 The reaction of a d-transition metal di-or polysulfide complex with a substituted alkyne has proved to be a very effective route, 7 e.g.…”
mentioning
confidence: 99%
“…5 Dithiolene ligands have been synthesised by several methods, including the combination of an alkyne with sulfur in a variety of its chemical forms. 5,6 The reaction of a d-transition metal di-or polysulfide complex with a substituted alkyne has proved to be a very effective route, 7 e.g. [Cp 2 Mo(S 4 )] 8 reacts with the alkynes RC 2 R 0 (R = C(O)Me; R 0 = a C(2)-substituted quinoxaline or a C(6)-substituted pterin) to produce the corresponding [Cp 2 Mo(S 2 C 2 RR 0 )] compound.…”
mentioning
confidence: 99%