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Structural and spectroscopic studies of rhodium-(I) and -(III) nitrato complexes

Journal Article


Abstract


  • Refluxing Rh(NO3)3·2H2O with an excess of PPh3 in MeOH or EtOH for over 48 h gives trans-[Rh(CO)(ONO2)(PPh3)2] 1 whereas the same reaction at room temperature gives predominantly [Rh(ONO2)(PPh 3)3] 2. X-Ray structure determinations of 1 and 2 show the nitrate groups to be monodentate in each case although disorder of the CO and NO3 groups in 1 precludes accurate determination of bond lengths and angles. There is no reaction of trans-[Rh(CO)X(PPh3)2] (X = Cl, F or ONO2) with H2 at room temperature and 1 atm pressure, whereas there is an immediate reaction of [Rh(ONO2) (PPh3)3] under the same conditions to give [RhH 2(ONO2)(PPh3)3] 3, which has been characterised by multinuclear NMR spectroscopy. Compound 3 loses PPh3 to give [RhH2(O2NO)(PPh3)2] 6a which has been characterised similarly and by X-ray crystallography; although the metal-bound hydrogens were not located the structure is clearly based on an octahedral geometry with trans phosphines and a bidentate nitrate.

Publication Date


  • 1992

Citation


  • Heaton, B. T., Iggo, J. A., Jacob, C., Blanchard, H., Hursthouse, M. B., Ghatak, I., . . . Villax, I. (1992). Structural and spectroscopic studies of rhodium-(I) and -(III) nitrato complexes. Journal of the Chemical Society, Dalton Transactions, (17), 2533-2537. doi:10.1039/DT9920002533

Scopus Eid


  • 2-s2.0-37049074478

Start Page


  • 2533

End Page


  • 2537

Issue


  • 17

Abstract


  • Refluxing Rh(NO3)3·2H2O with an excess of PPh3 in MeOH or EtOH for over 48 h gives trans-[Rh(CO)(ONO2)(PPh3)2] 1 whereas the same reaction at room temperature gives predominantly [Rh(ONO2)(PPh 3)3] 2. X-Ray structure determinations of 1 and 2 show the nitrate groups to be monodentate in each case although disorder of the CO and NO3 groups in 1 precludes accurate determination of bond lengths and angles. There is no reaction of trans-[Rh(CO)X(PPh3)2] (X = Cl, F or ONO2) with H2 at room temperature and 1 atm pressure, whereas there is an immediate reaction of [Rh(ONO2) (PPh3)3] under the same conditions to give [RhH 2(ONO2)(PPh3)3] 3, which has been characterised by multinuclear NMR spectroscopy. Compound 3 loses PPh3 to give [RhH2(O2NO)(PPh3)2] 6a which has been characterised similarly and by X-ray crystallography; although the metal-bound hydrogens were not located the structure is clearly based on an octahedral geometry with trans phosphines and a bidentate nitrate.

Publication Date


  • 1992

Citation


  • Heaton, B. T., Iggo, J. A., Jacob, C., Blanchard, H., Hursthouse, M. B., Ghatak, I., . . . Villax, I. (1992). Structural and spectroscopic studies of rhodium-(I) and -(III) nitrato complexes. Journal of the Chemical Society, Dalton Transactions, (17), 2533-2537. doi:10.1039/DT9920002533

Scopus Eid


  • 2-s2.0-37049074478

Start Page


  • 2533

End Page


  • 2537

Issue


  • 17