Nitrosyl complexes of rhenium

Abstract
The complex [ReCl2(N2COPh)(PPh3)2](I) reacts with nitrogen oxide to give the five-co-ordinate paramagnetic complex [ReCl2(NO)(PPh3)2](II) which adds other ligands, L, to form six-co-ordinate diamagnetic complexes [ReCl2(NO)(PPh3)2L](III). Generally tertiary phosphines (PR3) displace triphenylphosphine from (II) to give either [ReCl2(NO)(PR3)2] or [ReCl2(NO)(PR3)3], analogous to (II) and (III) respectively, depending on the bulk of the phosphine PR3, but dimethylphenylphosphine tends to give [ReCl2(NO)(PMe2Ph)2(PPh3)]. The nitrogen oxide in the above complexes is inert to attack by either electrophilic or nucleophilic reagents.

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