L. Chen et al., NITROSYLATION OF OCTAETHYLPORPHYRIN OSMIUM COMPLEXES WITH ALKYL NITRITES AND THIONITRITES - MOLECULAR-STRUCTURES OF 3 OSMIUM PORPHYRIN DERIVATIVES, Inorganic chemistry, 37(3), 1998, pp. 533-540
(OEP)Os(CO) reacts with n-butyl nitrite to give, after workup, the (OE
P)Os(NO)(O-n-Bu) trans addition product (OEP = octaethylporphyrinato d
ianion). Similarly, the reaction of (OEP)Os(CO) or [(OEP)Os](2) with i
soamyl nitrite gives the corresponding nitrosyl alkoxide, (OEP)Os(NO)(
O-i-C5H11). The related reactions of (OEP)Os(CO) or [(OEP)Os](2) with
isoamyl thionitrite gives the (OEP)Os(NO)(S-i-C5H11) nitrosyl thiolate
. The reaction of the [(OEP)Os](2)(PF6)(2) reagent with isoamyl thioni
trite gives the nitrosylation product, [(OEP)Os(NO)]PF6, which undergo
es anion hydrolysis to give the isolable difluorophosphate (OEP)Os(NO)
(O2PF2) derivative. Interestingly, the reaction of O2NC6H4N=NSPh with
[(OEP)Os](2) gives the (OEP)Os(SPh)(2) product with loss of the arylaz
o fragments. The solid-state structures of (OEP)Os(NO)(O-n-Bu), (OEP)O
s(NO)(O2PF2), and (OEP)Os(SPh)(2) have been determined by X-ray crysta
llography.