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

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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.

Original languageEnglish
Pages (from-to)3779-3786
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number19
Publication statusPublished - Oct 7 1996
Externally publishedYes

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Rhodium
Ethane
phosphine
Single crystals
Ligands
Water
X ray analysis
Bond length
Reaction products
Absorption spectra
X rays
Acids

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "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",
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.",
author = "Takayoshi Suzuki and Kiyoshi Isobe and Kazuo Kashiwabara and Junnosuke Fujita and Sumio Kaizaki",
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T1 - 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

AU - Suzuki, Takayoshi

AU - Isobe, Kiyoshi

AU - Kashiwabara, Kazuo

AU - Fujita, Junnosuke

AU - Kaizaki, Sumio

PY - 1996/10/7

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N2 - 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.

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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