Rhodium phosphinoether complexes. Part I. Crystal and molecular structures of trans-[1,5-bis(diphenylphosphino)-3-oxapentane-O,P,P′]-carbonylrhodium(I) hexafluorophosphate and trans-aqua[1,11-bis-(diphenylphosphino)-3,6,9-trioxaundecane-P,P′]carbonylrhodium(I)hexafluorophosphate

Abstract

The crystal and molecular structures of the title compounds (4) and (5) have been determined. Crystals of both are triclinic, space group P; data for (4) : a= 10.907(3), b= 11.047(2), c= 13.405(3)Å, α= 94.19(2), β= 82.30(2), γ= 107.98(2)°, Z= 2, 2 389 reflections, R 0.050; data for (5) : a= 9.837(2). b= 11.416(2). c= 17.554(3)Å, α= 94.08(2), β= 79.64(1), γ= 111.98(1)°, Z= 2, 3 106 reflections, R 0.057. Data were measured by diffractometer, and the structures solved by the heavy-atom methods. In both cations, the phosphorus atoms are co-ordinated trans[Rh–P, 2.300 Å in (4), 2.338 Å in (5)] with the carbonyl group (Rh–C, 1.77 Å)trans to an oxygen atom. In (4) this oxygen atom is the central atom of the phosphinoether (Rh–O 2.112 Å) but in (5) it is derived form a water molecule (Rh–O 2.107 Å) which is contained within the foruteen-membered ring, co-ordinated to the rhodium atom, and hydrogen bonded to two of the ring oxygen atoms.