Preparation and characterization of rhodium(III) complexes containing 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme). Structures of [RhX3(tdmme)] (X = Cl, Br or I), [Rh(NH3)3(tdmme)]3+ and [{Rh(tdmme)}2(μ-X)3]3+ (X = Cl or OH) in the solid state and in solution

Takayoshi Suzuki; Kiyoshi Isobe; Kazuo Kashiwabara; Junnosuke Fujita; Sumio Kaizaki

doi:10.1039/DT9960003779

Preparation and characterization of rhodium(III) complexes containing 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme). Structures of [RhX₃(tdmme)] (X = Cl, Br or I), [Rh(NH₃)₃(tdmme)]³⁺ and [{Rh(tdmme)}₂(μ-X)₃]³⁺ (X = Cl or OH) in the solid state and in solution

Takayoshi Suzuki, Kiyoshi Isobe, Kazuo Kashiwabara, Junnosuke Fujita, Sumio Kaizaki

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

Abstract

Several new rhodium(III) complexes containing a tripodal tridentate phosphine, MeC(CH₂PMe₂)₃ (tdmme), have been synthesized and their structures investigated both in the solid state and in solution. Single-crystal X-ray analyses revealed the smaller steric requirement and stronger trans influence of tdmme than those of the phenyl-substituted analogue, MeC(CH₂PPh₂)₃ (tdpme). The long Rh-Cl bond in the mononuclear trichloro complex, [RhCl₃(tdmme)] 1, due to the strong trans influence of tdmme, made the complex reactive in water; the structure of 1 in solution and its reaction products with some acids or bases were characterized. The triply chloro-bridged dinuclear complex, [{Rh(tdmme)}₂(μ-Cl)₃][BF₄]₃, also showed structural change in water, while the mononuclear triammine complex, [Rh(NH₃)₃(tdmme)][BF₄]₃, and the triply hydroxo-bridged dinuclear complex, [{Rh(tdmme)}₂(μ-OH)₃][BF₄]₃, were stable. The absorption spectra of the tdmme complexes suggested a stronger ligand field of tdmme to the rhodium(III) centre than those of corresponding didentate diphosphine ligands, in accordance with the short Rh-P bond lengths in 1 found by single-crystal X-ray analysis.

Original language	English
Pages (from-to)	3779-3786
Number of pages	8
Journal	Journal of the Chemical Society - Dalton Transactions
Issue number	19
DOIs	https://doi.org/10.1039/DT9960003779
Publication status	Published - Oct 7 1996
Externally published	Yes

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Chemistry(all)

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Suzuki, T., Isobe, K., Kashiwabara, K., Fujita, J., & Kaizaki, S. (1996). Preparation and characterization of rhodium(III) complexes containing 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme). Structures of [RhX₃(tdmme)] (X = Cl, Br or I), [Rh(NH₃)₃(tdmme)]³⁺ and [{Rh(tdmme)}₂(μ-X)₃]³⁺ (X = Cl or OH) in the solid state and in solution. Journal of the Chemical Society - Dalton Transactions, (19), 3779-3786. https://doi.org/10.1039/DT9960003779

Preparation and characterization of rhodium(III) complexes containing 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme). Structures of [RhX₃(tdmme)] (X = Cl, Br or I), [Rh(NH₃)₃(tdmme)]³⁺ and [{Rh(tdmme)}₂(μ-X)₃]³⁺ (X = Cl or OH) in the solid state and in solution. / Suzuki, Takayoshi; Isobe, Kiyoshi; Kashiwabara, Kazuo et al.
In: Journal of the Chemical Society - Dalton Transactions, No. 19, 07.10.1996, p. 3779-3786.

Research output: Contribution to journal › Article › peer-review

Suzuki, T, Isobe, K, Kashiwabara, K, Fujita, J & Kaizaki, S 1996, 'Preparation and characterization of rhodium(III) complexes containing 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme). Structures of [RhX₃(tdmme)] (X = Cl, Br or I), [Rh(NH₃)₃(tdmme)]³⁺ and [{Rh(tdmme)}₂(μ-X)₃]³⁺ (X = Cl or OH) in the solid state and in solution', Journal of the Chemical Society - Dalton Transactions, no. 19, pp. 3779-3786. https://doi.org/10.1039/DT9960003779

Suzuki T, Isobe K, Kashiwabara K, Fujita J, Kaizaki S. Preparation and characterization of rhodium(III) complexes containing 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme). Structures of [RhX₃(tdmme)] (X = Cl, Br or I), [Rh(NH₃)₃(tdmme)]³⁺ and [{Rh(tdmme)}₂(μ-X)₃]³⁺ (X = Cl or OH) in the solid state and in solution. Journal of the Chemical Society - Dalton Transactions. 1996 Oct 7;(19):3779-3786. doi: 10.1039/DT9960003779

Suzuki, Takayoshi ; Isobe, Kiyoshi ; Kashiwabara, Kazuo et al. / Preparation and characterization of rhodium(III) complexes containing 1,1,1-tris(dimethylphosphinomethyl)ethane (tdmme). Structures of [RhX₃(tdmme)] (X = Cl, Br or I), [Rh(NH₃)₃(tdmme)]³⁺ and [{Rh(tdmme)}₂(μ-X)₃]³⁺ (X = Cl or OH) in the solid state and in solution. In: Journal of the Chemical Society - Dalton Transactions. 1996 ; No. 19. pp. 3779-3786.

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abstract = "Several new rhodium(III) complexes containing a tripodal tridentate phosphine, MeC(CH2PMe2)3 (tdmme), have been synthesized and their structures investigated both in the solid state and in solution. Single-crystal X-ray analyses revealed the smaller steric requirement and stronger trans influence of tdmme than those of the phenyl-substituted analogue, MeC(CH2PPh2)3 (tdpme). The long Rh-Cl bond in the mononuclear trichloro complex, [RhCl3(tdmme)] 1, due to the strong trans influence of tdmme, made the complex reactive in water; the structure of 1 in solution and its reaction products with some acids or bases were characterized. The triply chloro-bridged dinuclear complex, [{Rh(tdmme)}2(μ-Cl)3][BF4]3, also showed structural change in water, while the mononuclear triammine complex, [Rh(NH3)3(tdmme)][BF4]3, and the triply hydroxo-bridged dinuclear complex, [{Rh(tdmme)}2(μ-OH)3][BF4]3, were stable. The absorption spectra of the tdmme complexes suggested a stronger ligand field of tdmme to the rhodium(III) centre than those of corresponding didentate diphosphine ligands, in accordance with the short Rh-P bond lengths in 1 found by single-crystal X-ray analysis.",

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AB - Several new rhodium(III) complexes containing a tripodal tridentate phosphine, MeC(CH2PMe2)3 (tdmme), have been synthesized and their structures investigated both in the solid state and in solution. Single-crystal X-ray analyses revealed the smaller steric requirement and stronger trans influence of tdmme than those of the phenyl-substituted analogue, MeC(CH2PPh2)3 (tdpme). The long Rh-Cl bond in the mononuclear trichloro complex, [RhCl3(tdmme)] 1, due to the strong trans influence of tdmme, made the complex reactive in water; the structure of 1 in solution and its reaction products with some acids or bases were characterized. The triply chloro-bridged dinuclear complex, [{Rh(tdmme)}2(μ-Cl)3][BF4]3, also showed structural change in water, while the mononuclear triammine complex, [Rh(NH3)3(tdmme)][BF4]3, and the triply hydroxo-bridged dinuclear complex, [{Rh(tdmme)}2(μ-OH)3][BF4]3, were stable. The absorption spectra of the tdmme complexes suggested a stronger ligand field of tdmme to the rhodium(III) centre than those of corresponding didentate diphosphine ligands, in accordance with the short Rh-P bond lengths in 1 found by single-crystal X-ray analysis.

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