Preparation and reactivity of half-sandwich organic azide complexes of osmium.

Organic azide complexes [Os(η5-C5H5)(κ1-N3R)(PPh3){P(OR1)3}]BPh4 (1, 2) [R = CH2C6H5 (a), CH2C6H4-4-CH3 (b), CH(CH3)C6H5 (c), C6H5 (d); R1 = Me (1), Et (2)] were prepared by allowing bromo-compounds [OsBr(η5-C5H5)(PPh3){P(OR1)3}] to react first with AgOTf and then with an excess of azide in toluene. Benzylazide complexes reacted in solution leading to imine derivatives [Os(η5-C5H5){κ1-NH[double bond, length as m-dash]C(R2)Ar}(PPh3){P(OR1)3}]BPh4 (3, 4) [R2 = H (a, b), CH3 (c); Ar = C6H5, C6H4-4-CH3; R1 = Me (3), Et (4)]. Phenylazide, on the other hand, reacted in solution affording the dinuclear dinitrogen complex [{Os(η5-C5H5)(PPh3)[P(OMe)3]}2(μ-N2)](BPh4)2 (5).