Darstellung,Strukturen und EPR-Spektren der Rhenium(II)-Nitrosylkomplexe [Re(NO)Cl2(PPh3)(OPPh3)(OReO3)], [Re(NO)Cl2(OPPh3)2(OReO3)] und [Re(NO)Cl2(OPPh3)3](ReO4)

Synthesis, Structures, and EPR-Spectra of the Rhenium(II) Nitrosyl Complexes Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)], Re(NO)Cl₂(OPPh₃)₂(OReO₃)], and Re(NO)Cl₂(OPPh₃)₃](ReO₄) The paramagnetic rhenium(II) nitrosyl complexes Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)], Re(NO)Cl₂(OPPh₃)₂ · (OReO₃)], and Re(NO)Cl₂(OPPh₃)₃](ReO₄) are formed during the reaction of ReOCl₃(PPh₃)₂] with NO gas in CH₂Cl₂/EtOH. These and two other Re^II complexes with 5 d⁵ ”︁low-spin”︁”︁-configuration can be observed during the reaction EPR spectroscopically. Crystal structure analysis shows linear coordinated NO ligands (Re–N–O-angles between 171.9 and 177.3°). Three OPPh₃ ligands are meridionally coordinated in the final product of the reaction, Re(NO)Cl₂(OPPh₃)₃]ReO₄] (monoclinic, P2₁/c, a = 13.47(1), b = 17.56(1), c = 24.69(2) Å, β = 95.12(4)°, Z = 4). Re(NO)Cl₂(PPh₃)(OPPh₃)(OReO₃)] (triclinic P 1, a = 10.561(6), b = 11.770(4), c = 18.483(8) Å, α = 77.29(3), β = 73.53(3), γ = 64.70(4)°, Z = 2) and Re(NO)Cl₂ (OPPh₃)₂(OReO₃)] (monoclinic P2₁/c, a = 10.652(1), b = 31.638(4), c = 11.886(1) Å, β = 115.59(1)°), Z = 4) can be isolated at shorter reaction times besides the complexes Re(NO)Cl₃(Ph₃P)₂], Re(NO)Cl₃(Ph₃P) · (Ph₃PO)], and ReCl₄(Ph₃P)₂].