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 J.
AU - Churchill, Melvyn Rowen
AU - Takeuchi, Kenneth J.
N1 - Funding Information:
We (K.J.T.) gratefully acknowledge Johnson Matthey Aesar/Alfa for the generous loan of the RuC13 • 3H20. Financial support was provided by the National Science Foundation (Grant CHE 9120602) (K.J.T.) and the ARCO Chemical Corp. (K.J.T.). Purchase of the Siemens R3m/V diffractometer was made possible by Grant 89-13733 (M.R.C.) from the Chemical Instrumentation Program of the National Science Foundation.
PY - 1995/11
Y1 - 1995/11
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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U2 - 10.1016/0020-1693(95)04715-8
DO - 10.1016/0020-1693(95)04715-8
M3 - Article
AN - SCOPUS:0002914518
SN - 0020-1693
VL - 239
SP - 77
EP - 85
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1-2
ER -