- Synthesis and properties of the first disulfur and diselenium complexes of platinum
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The reactions of overcrowded platinum(0) complexes [Pt{P(Ar)Me 2}2] (Ar = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt), 2,6-bis[bis-(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt)) with elemental sulfur and selenium resulted in the formation of the first platinum disulfur and diselenium complexes, [Pt(S2){P(Ar)Me 2}2] (4a (Ar = Tbt), 4b (Ar = Bbt) and [Pt(Se 2){P(Ar)Me2}2] (5a (Ar = Tbt), 5b (Ar = Bbt)) respectively. The x-ray crystallographic analyses of 4b and 56 showed a novel three-membered PtE2 (E = S, Se) ring structure with a square planar geometry around the platinum center. The oxidation of 4b and 5b with an equimolar amount of m-chloroperbenzoic acid or tert-butyl hydroperoxide in dichloromethane yielded the corresponding disulfur and diselenium monoxide complexes [Pt(E2O){P(Bbt)Me2}2] (6 (E = S), 7 (E = Se)). The further reactions of 6 and 7 with an excess of oxidants gave the corresponding O,S-coordinated thiosulfato complex [Pt(S2O 3){P(Bbt)Me2}2] (8) and the O,O-coordinated selenito complex [Pt(SeO3){P(Bbt)Me2}2] (11), respectively. The dynamic behavior in solution was revealed by the variable-temperature NMR spectroscopy for 4b, 5b, 8, and 11, which indicates the existence of the intramolecular CH...E (E = O, S, Se) interactions between the methine hydrogens of the o-bis(trimethylsilyl)methyl groups and the Pt-bonded chalcogen atoms.
- Tokitoh, Norihiro,Nagata, Kazuto,Takeda, Nobuhiro
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p. 915 - 927
(2007/10/03)
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- Synthesis, structure, and properties of the first disulfur and diselenium complexes of platinum
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The first platinum disulfur and diselenium complexes, [Pt(S 2)(ArMe2P)2] (Ar = Tbt (4a), Bbt (4b)) and [Pt(Se 2)(ArMe2P)2] (Ar = Tbt (5a), Bbt (5b)), have been synthesized by the reactions of the corresponding overcrowded platinum(0) complexes [Pt(ArMe2P)2] with elemental sulfur and selenium. Molecular structures of 4b and 5b were established by X-ray crystallographic analyses, which show a novel three-membered PtE2 (E = S, Se) ring structure with a square planar geometry around the platinum center. The oxidation of 4b and 5b with an equimolar amount of m-chloroperbenzoic acid or tert-butyl hydroperoxide in dichloromethane afforded the corresponding disulfur and diselenium monoxide complexes [Pt(E 2O)(BbtMe2P)2] (E = S (6), Se (7)), respectively. An interesting difference in reactivity between 6 and 7 was shown in the further reactions with an excess of oxidants, which produced the corresponding O,S-coordinated thiosulfate complex [Pt(S2O 3)(BbtMe2P)2] (8) and the O,O-coordinated selenite complex [Pt(SeO3)(BbtMe2P)2] (11), respectively. The dynamic behavior in solution was revealed by the variable-temperature NMR spectroscopy for 4b, 5b, 8, and 11, which indicates the existence of the intramolecular CH...E (E = O, S, Se) interactions between the methine hydrogens of the o-bis(trimethylsilyl)methyl groups and the Pt-bonded heteroatoms.
- Nagata, Kazuto,Takeda, Nobuhiro,Tokitoh, Norihiro
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p. 1577 - 1587
(2007/10/03)
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- The first disulfur and diselenium complexes of platinum: Syntheses and crystal structures
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Rings with platinum: The first platinum disulfur and diselenium complexes have been synthesized by taking advantage of new phosphane ligands bearing an extremely bulky substituent (see structure). The molecular structures of the disulfur and diselenium co
- Nagata, Kazuto,Takeda, Nobuhiro,Tokitoh, Norihiro
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p. 136 - 138
(2007/10/03)
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- Synthesis of novel platinum dichalcogenido-complexes by taking advantage of bulky phosphine ligands
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The first stable disulfido and diselenido complexes of platinum-bearing bulky phosphine ligands were synthesized by the reaction of the corresponding zerovalent platinum complexes with elemental sulfur and selenium, respectively. The molecular structures
- Nagata, Kazuto,Takeda, Nobuhiro,Tokitoh, Norihiro
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p. 1859 - 1862
(2007/10/03)
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