Preparation, crystal structures and spectroscopic properties of novel [MIIICl3 - N(P)3 + n]n+ (M = Co, Rh; N = 0, 1, 2 or 3) series of complexes containing tripodal tridentate phosphine, 1,1,1-tris(dimethylphosphinomethyl)ethane

Takayoshi Suzuki, Toshiaki Tsukuda, Masakazu Kiki, Sumio Kaizaki, Kiyoshi Isobe, Hideo D. Takagi, Kazuo Kashiwabara

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Cobalt(III) and rhodium(III) complexes of the series of [M IIICl3 - n(P)3 + n]n+ (M = Co or Rh; n = 0, 1, 2 or 3) have been prepared with the use of 1,1,1- tris(dimethylphosphinomethyl)ethane (tdmme) and mono- or didentate phosphines. The single-crystal X-ray analyses of both series of complexes revealed that the M-P and M-Cl bond lengths were dependent primarily on the strong trans influence of the phosphines, and secondarily on the steric congestion around the metal center resulting from the coordination of several phosphine groups. In fact, the M-P(tdmme) bonds became longer in the order of [MCl3(tdmme)] <[MCl2(tdmme)(PMe3)]+ <[MCl(tdmme)(dmpe)] 2+ (dmpe = 1,2-bis(dimethylphosphino)ethane) <[M(tdmme) 2]3+ for both CoIII and RhIII series of complexes, while the M-Cl bond lengths were shortened in this order (except for [M(tdmme)2]3+). Such a steric congestion around the metal center can also account for the structural and spectroscopic characteristics of the series of complexes, [MCl(tdmme)(dmpm, dmpe or dmpp)]2+ (dmpm = bis(dimethylphosphino)methane, dmpp = 1,3-bis(dimethylphosphino)propane). The X-ray analysis for [CoCl(tdmme)(dmpm or dmpe)](BF4)2 showed that all Co-P bonds in the dmpm complex were shorter by 0.03-0.04 Å than those in the dmpe complex. Furthermore, the first d-d transition energy of the CoIII complexes and the 1JRh-P(tdmme) coupling constants observed for the RhIII complexes indicated an unusual order in the coordination bond strengths of the didentate diphosphines, i.e., dmpm > dmpe > dmpp.

Original languageEnglish
Pages (from-to)2501-2512
Number of pages12
JournalInorganica Chimica Acta
Volume358
Issue number8
DOIs
Publication statusPublished - May 2 2005
Externally publishedYes

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phosphine
Ethane
phosphines
ethane
Phosphines
Crystal structure
preparation
crystal structure
Rhodium
congestion
Bond length
Cobalt
rhodium
cobalt
Metals
X-Rays
Single crystals
X rays
single crystals
metals

Keywords

  • Cobalt(III) and rhodium(III) complexes
  • Crystal structures
  • Steric congestion
  • Trans influence
  • Tripodal tridentate phosphine

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Preparation, crystal structures and spectroscopic properties of novel [MIIICl3 - N(P)3 + n]n+ (M = Co, Rh; N = 0, 1, 2 or 3) series of complexes containing tripodal tridentate phosphine, 1,1,1-tris(dimethylphosphinomethyl)ethane. / Suzuki, Takayoshi; Tsukuda, Toshiaki; Kiki, Masakazu; Kaizaki, Sumio; Isobe, Kiyoshi; Takagi, Hideo D.; Kashiwabara, Kazuo.

In: Inorganica Chimica Acta, Vol. 358, No. 8, 02.05.2005, p. 2501-2512.

Research output: Contribution to journalArticle

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abstract = "Cobalt(III) and rhodium(III) complexes of the series of [M IIICl3 - n(P)3 + n]n+ (M = Co or Rh; n = 0, 1, 2 or 3) have been prepared with the use of 1,1,1- tris(dimethylphosphinomethyl)ethane (tdmme) and mono- or didentate phosphines. The single-crystal X-ray analyses of both series of complexes revealed that the M-P and M-Cl bond lengths were dependent primarily on the strong trans influence of the phosphines, and secondarily on the steric congestion around the metal center resulting from the coordination of several phosphine groups. In fact, the M-P(tdmme) bonds became longer in the order of [MCl3(tdmme)] <[MCl2(tdmme)(PMe3)]+ <[MCl(tdmme)(dmpe)] 2+ (dmpe = 1,2-bis(dimethylphosphino)ethane) <[M(tdmme) 2]3+ for both CoIII and RhIII series of complexes, while the M-Cl bond lengths were shortened in this order (except for [M(tdmme)2]3+). Such a steric congestion around the metal center can also account for the structural and spectroscopic characteristics of the series of complexes, [MCl(tdmme)(dmpm, dmpe or dmpp)]2+ (dmpm = bis(dimethylphosphino)methane, dmpp = 1,3-bis(dimethylphosphino)propane). The X-ray analysis for [CoCl(tdmme)(dmpm or dmpe)](BF4)2 showed that all Co-P bonds in the dmpm complex were shorter by 0.03-0.04 {\AA} than those in the dmpe complex. Furthermore, the first d-d transition energy of the CoIII complexes and the 1JRh-P(tdmme) coupling constants observed for the RhIII complexes indicated an unusual order in the coordination bond strengths of the didentate diphosphines, i.e., dmpm > dmpe > dmpp.",
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T1 - Preparation, crystal structures and spectroscopic properties of novel [MIIICl3 - N(P)3 + n]n+ (M = Co, Rh; N = 0, 1, 2 or 3) series of complexes containing tripodal tridentate phosphine, 1,1,1-tris(dimethylphosphinomethyl)ethane

AU - Suzuki, Takayoshi

AU - Tsukuda, Toshiaki

AU - Kiki, Masakazu

AU - Kaizaki, Sumio

AU - Isobe, Kiyoshi

AU - Takagi, Hideo D.

AU - Kashiwabara, Kazuo

PY - 2005/5/2

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N2 - Cobalt(III) and rhodium(III) complexes of the series of [M IIICl3 - n(P)3 + n]n+ (M = Co or Rh; n = 0, 1, 2 or 3) have been prepared with the use of 1,1,1- tris(dimethylphosphinomethyl)ethane (tdmme) and mono- or didentate phosphines. The single-crystal X-ray analyses of both series of complexes revealed that the M-P and M-Cl bond lengths were dependent primarily on the strong trans influence of the phosphines, and secondarily on the steric congestion around the metal center resulting from the coordination of several phosphine groups. In fact, the M-P(tdmme) bonds became longer in the order of [MCl3(tdmme)] <[MCl2(tdmme)(PMe3)]+ <[MCl(tdmme)(dmpe)] 2+ (dmpe = 1,2-bis(dimethylphosphino)ethane) <[M(tdmme) 2]3+ for both CoIII and RhIII series of complexes, while the M-Cl bond lengths were shortened in this order (except for [M(tdmme)2]3+). Such a steric congestion around the metal center can also account for the structural and spectroscopic characteristics of the series of complexes, [MCl(tdmme)(dmpm, dmpe or dmpp)]2+ (dmpm = bis(dimethylphosphino)methane, dmpp = 1,3-bis(dimethylphosphino)propane). The X-ray analysis for [CoCl(tdmme)(dmpm or dmpe)](BF4)2 showed that all Co-P bonds in the dmpm complex were shorter by 0.03-0.04 Å than those in the dmpe complex. Furthermore, the first d-d transition energy of the CoIII complexes and the 1JRh-P(tdmme) coupling constants observed for the RhIII complexes indicated an unusual order in the coordination bond strengths of the didentate diphosphines, i.e., dmpm > dmpe > dmpp.

AB - Cobalt(III) and rhodium(III) complexes of the series of [M IIICl3 - n(P)3 + n]n+ (M = Co or Rh; n = 0, 1, 2 or 3) have been prepared with the use of 1,1,1- tris(dimethylphosphinomethyl)ethane (tdmme) and mono- or didentate phosphines. The single-crystal X-ray analyses of both series of complexes revealed that the M-P and M-Cl bond lengths were dependent primarily on the strong trans influence of the phosphines, and secondarily on the steric congestion around the metal center resulting from the coordination of several phosphine groups. In fact, the M-P(tdmme) bonds became longer in the order of [MCl3(tdmme)] <[MCl2(tdmme)(PMe3)]+ <[MCl(tdmme)(dmpe)] 2+ (dmpe = 1,2-bis(dimethylphosphino)ethane) <[M(tdmme) 2]3+ for both CoIII and RhIII series of complexes, while the M-Cl bond lengths were shortened in this order (except for [M(tdmme)2]3+). Such a steric congestion around the metal center can also account for the structural and spectroscopic characteristics of the series of complexes, [MCl(tdmme)(dmpm, dmpe or dmpp)]2+ (dmpm = bis(dimethylphosphino)methane, dmpp = 1,3-bis(dimethylphosphino)propane). The X-ray analysis for [CoCl(tdmme)(dmpm or dmpe)](BF4)2 showed that all Co-P bonds in the dmpm complex were shorter by 0.03-0.04 Å than those in the dmpe complex. Furthermore, the first d-d transition energy of the CoIII complexes and the 1JRh-P(tdmme) coupling constants observed for the RhIII complexes indicated an unusual order in the coordination bond strengths of the didentate diphosphines, i.e., dmpm > dmpe > dmpp.

KW - Cobalt(III) and rhodium(III) complexes

KW - Crystal structures

KW - Steric congestion

KW - Trans influence

KW - Tripodal tridentate phosphine

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