Synthesis and Reactions of Group 6 Metal Half-Sandwich Complexes of 2,2-Dicyanoethylene-1,1-dichalcogenolates [(Cp[sup *])M{E[sub 2]C = C(CN)[sub 2]}[sub 2]][sup -] (M = Mo, W; E = S, Se).
In: Inorganic Chemistry, Jg. 41 (2002-09-09), Heft 18, S. 4824-4833
academicJournal
Zugriff:
A series of group 6 transition metal half-sandwich complexes with 1,1-dichalcogenide ligands have been prepared by the reactions of Cp[sup *]MCI[sub 4] (Cp[sup *] = η[sup 5]-C[sub 5]Me[sub 5]; M = Mo, W) with the potassium salt of 2,2-dicyanoethylene-1,1dithiolate, (KS)[sub 2]C=C(CN)[sub 2] (K[sub 2]-i-mnt), or the analogous seleno compound, (KSe)[sub 2]C=C(CN)[sub 2] (K[sub 2]-i-mas). The reaction of Cp[sup *]MCI[sub 4] with (KS)[sub 2]C=C(CN)[sub 2] in a 1:3 molar ratio in CH[sub 3]CN gave rise to K[Cp[sup *]M{S[sub 2]C=C(CN)[sub 2]}[sub 2]] (M = Mo, 1a, 74%; M = W, 2a, 46%). Under the same conditions, the reaction of Cp[sup *]MoCl[sub 4] with 3 equiv of (KSe)[sub 2]C= C(CN)[sub 2] afforded K[Cp[sup *]Mo{ Se[sub 2]C=C(CN)[sub 2]}[sub 2]] (3a) and K[Cp[sup *]Mo{Se[sub 2]C=C(CN)[sub 2]}{Se(Se[sub 2])C=C(CN)2}] (4)in respective yields of 45% and 25%. Cation exchange reactions of 1a, 2a, and 3a with Et[sub 4]NBr resulted in isolation of (Et[sub 4]N)[Cp[sup *]Mo{S[sub 2]C=C(CN)[sub 2]}[sub 2]] (1b), (Et[sub 4]N)[Cp[sup *]W{S[sub 2]C=C(CN)[sub 2]}[sub 2]] (2b), and (Et[sub 4]N)[Cp[sup *]Mo{Se[sub 2]C=C(CN)[sub 2]}[sub 2]] (3b), respectively. Complex 4 crystallized with one THF and one CH[sub 3]CN molecule as a three-dimensional network structure. inspection of the reaction of Cp[sub *]WCI[sub 4] with (KSe)[sub 2]C=C(CN)[sub 2] by ESI-MS revealed the existence of three species in CH[sub 3]CN, [Cp[sup *]W{Se[sub 2]C=C(CN)[sub 2]}[sub 2].] , [Cp[sup *]W{Se[sub 2]C==C(CN)[sub 2]}{Se(Se[sub 2])C=C(CN)[sub 2]}], and [Cp[sup *]W{Se(Se[sub 2])C=C(CN)[sub 2]}[sub 2][sup -], of which [Cp[sup *]W{Se[sub 2]C=C(CN)[sub 2]}{Se(Se[sub 2])C=C(CN)[sub 2]}] (5) was isolated as the main product. Treatment of 2a with ¼ equiv of S[sub 8] in refluxing THF resulted in sulfur insertion and gave rise to K[Cp[sup *]W{S[sub 2]C=C(CN)[sub 2]}{S(S[sub 2])C= C(CN)[sub 2]}] (6), which crystallized with two THF molecules forming a three-dimensional network structure. 6 can also be... [ABSTRACT FROM AUTHOR]
Titel: |
Synthesis and Reactions of Group 6 Metal Half-Sandwich Complexes of 2,2-Dicyanoethylene-1,1-dichalcogenolates [(Cp[sup *])M{E[sub 2]C = C(CN)[sub 2]}[sub 2]][sup -] (M = Mo, W; E = S, Se).
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Autor/in / Beteiligte Person: | Hong, Maochun ; Cao, Rong ; Kawaguchi, Hiroyuki ; Tatsumi, Kazuyuki |
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Zeitschrift: | Inorganic Chemistry, Jg. 41 (2002-09-09), Heft 18, S. 4824-4833 |
Veröffentlichung: | 2002 |
Medientyp: | academicJournal |
ISSN: | 0020-1669 (print) |
DOI: | 10.1021/ic025609a |
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