Crystal structures of trans-[Ru(dppe)2(CO)(Cl)](BF4)·2(toluene) and trans-[Ru(dppm)2(CO)(Cl)](BF4)·CH2Cl2: a study of the steric and electronic ligand effects of trans-positioned diphosphine ligands

Lisa F. Szczepura, Julia Giambra, Ronald F. See, Holly Lawson, Thomas S. Janik, Alan John Jircitano, Melvyn Rowen Churchill, Kenneth J. Takeuchi

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Abstract

Single-crystal X-ray diffraction studies were carried out on the complexes trans-[Ru(dppe)2(CO)(Cl)](BF4) ·2(toluene) (1) (where dppe = 1,2-bis(diphenylphosphino)ethane) and trans-[Ru(dppm)2(CO)(Cl)](BF4) ·CH2Cl2 (2) (where dppm = bis(diphenylphosphino)methane). Complex 1 crystallizes in the orthorhombic space group P21212 with a = 14.366(3), b = 17.075(3), c = 12.433(2) A ̊, V = 3049.8(10) A ̊3 and Z = 2. The structure was refined to R = 3.02% for 3233 reflections above 6σ (R = 4.46% for all 3991 point-group independent data); the Ru-cation lies on a site of C2 symmetry, leading to disorder of the Cl and CO ligands. Complex 2 crystallizes in the orthorhombic space group Pna21, with a = 22.425(7), b = 11.515(4), c = 19.511(10) A ̊, V = 5038(3) A ̊3 and Z = 4. The structure was refined to R = 4.43% for 4770 reflections above 6σ (R = 7.09% for all 6631 point-group independent data). The crystal structure data suggest increased intramolecular interligand interactions with the trans-bis(dppe) complexes relative to the trans-bis(dppm) complexes. In order to furth assess the steric ligand effects of dppm and dppe on the redox chemistry of ruthenium complexes, the electrochemical data for complexes 1 and 2 as well as for trans-Ru(dppe)2(Cl)2 and trans-Ru(dppm)2(Cl)2 were analyzed. The Epa value for the oxidation of complex 1 was more positive than the Epa value for the oxidation of complex 2; similarly, the E 1 2 value for the oxidation of trans-Ru(dppe)2(Cl)2 was more positive than the E 1 2 value for the oxidation of trans-Ru(dppm)2(Cl)2. The increase in the redox potentials for the oxidation of the dope complexes may be due to the enhanced intramolecular interligand interactions of the dppe ligands, which is in agreement with the crystal structure data.

Original languageEnglish (US)
Pages (from-to)77-85
Number of pages9
JournalInorganica Chimica Acta
Volume239
Issue number1-2
DOIs
StatePublished - Jan 1 1995

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Toluene
Carbon Monoxide
toluene
Crystal structure
Ligands
Oxidation
ligands
oxidation
crystal structure
Point groups
electronics
Ethane
Ruthenium
ethane
Methane
ruthenium
methane
Positive ions
dichlorotetrakis(dimethyl sulfoxide)ruthenium II
Cations

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Szczepura, Lisa F. ; Giambra, Julia ; See, Ronald F. ; Lawson, Holly ; Janik, Thomas S. ; Jircitano, Alan John ; Churchill, Melvyn Rowen ; Takeuchi, Kenneth J. / Crystal structures of trans-[Ru(dppe)2(CO)(Cl)](BF4)·2(toluene) and trans-[Ru(dppm)2(CO)(Cl)](BF4)·CH2Cl2 : a study of the steric and electronic ligand effects of trans-positioned diphosphine ligands. In: Inorganica Chimica Acta. 1995 ; Vol. 239, No. 1-2. pp. 77-85.
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abstract = "Single-crystal X-ray diffraction studies were carried out on the complexes trans-[Ru(dppe)2(CO)(Cl)](BF4) ·2(toluene) (1) (where dppe = 1,2-bis(diphenylphosphino)ethane) and trans-[Ru(dppm)2(CO)(Cl)](BF4) ·CH2Cl2 (2) (where dppm = bis(diphenylphosphino)methane). Complex 1 crystallizes in the orthorhombic space group P21212 with a = 14.366(3), b = 17.075(3), c = 12.433(2) A ̊, V = 3049.8(10) A ̊3 and Z = 2. The structure was refined to R = 3.02{\%} for 3233 reflections above 6σ (R = 4.46{\%} for all 3991 point-group independent data); the Ru-cation lies on a site of C2 symmetry, leading to disorder of the Cl and CO ligands. Complex 2 crystallizes in the orthorhombic space group Pna21, with a = 22.425(7), b = 11.515(4), c = 19.511(10) A ̊, V = 5038(3) A ̊3 and Z = 4. The structure was refined to R = 4.43{\%} for 4770 reflections above 6σ (R = 7.09{\%} for all 6631 point-group independent data). The crystal structure data suggest increased intramolecular interligand interactions with the trans-bis(dppe) complexes relative to the trans-bis(dppm) complexes. In order to furth assess the steric ligand effects of dppm and dppe on the redox chemistry of ruthenium complexes, the electrochemical data for complexes 1 and 2 as well as for trans-Ru(dppe)2(Cl)2 and trans-Ru(dppm)2(Cl)2 were analyzed. The Epa value for the oxidation of complex 1 was more positive than the Epa value for the oxidation of complex 2; similarly, the E 1 2 value for the oxidation of trans-Ru(dppe)2(Cl)2 was more positive than the E 1 2 value for the oxidation of trans-Ru(dppm)2(Cl)2. The increase in the redox potentials for the oxidation of the dope complexes may be due to the enhanced intramolecular interligand interactions of the dppe ligands, which is in agreement with the crystal structure data.",
author = "Szczepura, {Lisa F.} and Julia Giambra and See, {Ronald F.} and Holly Lawson and Janik, {Thomas S.} and Jircitano, {Alan John} and Churchill, {Melvyn Rowen} and Takeuchi, {Kenneth J.}",
year = "1995",
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doi = "10.1016/0020-1693(95)04715-8",
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Crystal structures of trans-[Ru(dppe)2(CO)(Cl)](BF4)·2(toluene) and trans-[Ru(dppm)2(CO)(Cl)](BF4)·CH2Cl2 : a study of the steric and electronic ligand effects of trans-positioned diphosphine ligands. / Szczepura, Lisa F.; Giambra, Julia; See, Ronald F.; Lawson, Holly; Janik, Thomas S.; Jircitano, Alan John; Churchill, Melvyn Rowen; Takeuchi, Kenneth J.

In: Inorganica Chimica Acta, Vol. 239, No. 1-2, 01.01.1995, p. 77-85.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Crystal structures of trans-[Ru(dppe)2(CO)(Cl)](BF4)·2(toluene) and trans-[Ru(dppm)2(CO)(Cl)](BF4)·CH2Cl2

T2 - a study of the steric and electronic ligand effects of trans-positioned diphosphine ligands

AU - Szczepura, Lisa F.

AU - Giambra, Julia

AU - See, Ronald F.

AU - Lawson, Holly

AU - Janik, Thomas S.

AU - Jircitano, Alan John

AU - Churchill, Melvyn Rowen

AU - Takeuchi, Kenneth J.

PY - 1995/1/1

Y1 - 1995/1/1

N2 - Single-crystal X-ray diffraction studies were carried out on the complexes trans-[Ru(dppe)2(CO)(Cl)](BF4) ·2(toluene) (1) (where dppe = 1,2-bis(diphenylphosphino)ethane) and trans-[Ru(dppm)2(CO)(Cl)](BF4) ·CH2Cl2 (2) (where dppm = bis(diphenylphosphino)methane). Complex 1 crystallizes in the orthorhombic space group P21212 with a = 14.366(3), b = 17.075(3), c = 12.433(2) A ̊, V = 3049.8(10) A ̊3 and Z = 2. The structure was refined to R = 3.02% for 3233 reflections above 6σ (R = 4.46% for all 3991 point-group independent data); the Ru-cation lies on a site of C2 symmetry, leading to disorder of the Cl and CO ligands. Complex 2 crystallizes in the orthorhombic space group Pna21, with a = 22.425(7), b = 11.515(4), c = 19.511(10) A ̊, V = 5038(3) A ̊3 and Z = 4. The structure was refined to R = 4.43% for 4770 reflections above 6σ (R = 7.09% for all 6631 point-group independent data). The crystal structure data suggest increased intramolecular interligand interactions with the trans-bis(dppe) complexes relative to the trans-bis(dppm) complexes. In order to furth assess the steric ligand effects of dppm and dppe on the redox chemistry of ruthenium complexes, the electrochemical data for complexes 1 and 2 as well as for trans-Ru(dppe)2(Cl)2 and trans-Ru(dppm)2(Cl)2 were analyzed. The Epa value for the oxidation of complex 1 was more positive than the Epa value for the oxidation of complex 2; similarly, the E 1 2 value for the oxidation of trans-Ru(dppe)2(Cl)2 was more positive than the E 1 2 value for the oxidation of trans-Ru(dppm)2(Cl)2. The increase in the redox potentials for the oxidation of the dope complexes may be due to the enhanced intramolecular interligand interactions of the dppe ligands, which is in agreement with the crystal structure data.

AB - Single-crystal X-ray diffraction studies were carried out on the complexes trans-[Ru(dppe)2(CO)(Cl)](BF4) ·2(toluene) (1) (where dppe = 1,2-bis(diphenylphosphino)ethane) and trans-[Ru(dppm)2(CO)(Cl)](BF4) ·CH2Cl2 (2) (where dppm = bis(diphenylphosphino)methane). Complex 1 crystallizes in the orthorhombic space group P21212 with a = 14.366(3), b = 17.075(3), c = 12.433(2) A ̊, V = 3049.8(10) A ̊3 and Z = 2. The structure was refined to R = 3.02% for 3233 reflections above 6σ (R = 4.46% for all 3991 point-group independent data); the Ru-cation lies on a site of C2 symmetry, leading to disorder of the Cl and CO ligands. Complex 2 crystallizes in the orthorhombic space group Pna21, with a = 22.425(7), b = 11.515(4), c = 19.511(10) A ̊, V = 5038(3) A ̊3 and Z = 4. The structure was refined to R = 4.43% for 4770 reflections above 6σ (R = 7.09% for all 6631 point-group independent data). The crystal structure data suggest increased intramolecular interligand interactions with the trans-bis(dppe) complexes relative to the trans-bis(dppm) complexes. In order to furth assess the steric ligand effects of dppm and dppe on the redox chemistry of ruthenium complexes, the electrochemical data for complexes 1 and 2 as well as for trans-Ru(dppe)2(Cl)2 and trans-Ru(dppm)2(Cl)2 were analyzed. The Epa value for the oxidation of complex 1 was more positive than the Epa value for the oxidation of complex 2; similarly, the E 1 2 value for the oxidation of trans-Ru(dppe)2(Cl)2 was more positive than the E 1 2 value for the oxidation of trans-Ru(dppm)2(Cl)2. The increase in the redox potentials for the oxidation of the dope complexes may be due to the enhanced intramolecular interligand interactions of the dppe ligands, which is in agreement with the crystal structure data.

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