Pentamethylcyclopentadienyl osmium complexes that contain diazoalkane, dioxygen and allenylidene ligands: preparation and reactivity.

Diazoalkane complexes [Os(η5-C5Me5)(N2CAr1Ar2)(PPh3){P(OR)3}]BPh4 (1, 2) [R = Me (1), Et (2); Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (fluorenyl) (c)] were prepared by reacting bromo-compounds OsBr(η5-C5Me5)(PPh3){P(OR)3} with an excess of diazoalkane in ethanol. The treatment of diazoalkane complexes 1 and 2 with acetylene under mild conditions (1 atm, RT) led to dipolar (3 + 2) cycloaddition affording 3H-pyrazole derivatives [Os(η5-C5Me5)(η1-[upper bond 1 start]N[double bond, length as m-dash]NC(C12H8)CH[double bond, length as m-dash]C[upper bond 1 end]H)(PPh3){P(OR)3}]BPh4 (6, 7) [R = Me (6), Et (7)] whereas reactions with terminal alkynes R1C[triple bond, length as m-dash]CH (R1 = Ph, p-tolyl, COOMe) gave vinylidene derivatives [Os(η5-C5Me5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)R1}(PPh3){P(OR)3}]BPh4 (8b-d, 9b-d) [R = Me (8), Et (9); R1 = Ph (b), p-tolyl (c), COOMe (d)]. Exposure to air of dichloromethane solutions of complexes 1 and 2 produced dioxygen derivatives [Os(η5-C5Me5)(η2-O2)(PPh3){P(OR)3}]BPh4 (10, 11) [R = Me (10), Et (11)]. Allenylidene [Os][double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]CR1R2 (12-14) [R1 = R2 = Ph (12, 13); R1 = Ph, R2 = Me (14)], vinylvinylidene [Os][double bond, length as m-dash]C[double bond, length as m-dash]C(H)C(Ph)[double bond, length as m-dash]CH2 (15) and 3-hydroxyvinylidene [Os][double bond, length as m-dash]C[double bond, length as m-dash]C(H)C(H)R2(OH) (16, 17) [R2 = Ph (16), H (17)] derivatives were also prepared. The vinylidene complex [Os(η5-C5Me5)([double bond, length as m-dash]C[double bond, length as m-dash]CH2)(PPh3){P(OMe)3}]BPh4 (8a) reacted with PPh3 to afford the alkenylphosphonium derivative [Os(η5-C5Me5){η1-C(H)[double bond, length as m-dash]C(H)PPh3}(PPh3){P(OMe)3}]BPh4 (18) whereas vinylidene complexes 8 and 9 reacted with water leading to the hydrolysis of the alkyne and the formation of carbonyl complexes [Os(η5-C5Me5)(CO)(PPh3){P(OR)3}]BPh4 (19, 20). The complexes were characterised by spectroscopic data (IR and NMR) and by X-ray crystal structure determination of [Os(η5-C5Me5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)p-tolyl}(PPh3){P(OEt)3}]BPh4 (9c), [Os(η5-C5Me5)(η2-O2)(PPh3){P(OMe)3}]BPh4 (10) and [Os(η5-C5Me5)(CO)(PPh3){P(OMe)3}]BPh4 (19).