120022-48-2Relevant academic research and scientific papers
Reactivity of the homoleptic osmium aryl Os(2-MeC6H4)4: Ligand-induced reductive coupling, σ- to π-rearrangement, and ortho-hydrogen activation
Arnold, John,Wilkinson, Geoffrey,Hussain, Bilquis,Hursthouse, Michael B.
, p. 1362 - 1369 (2008/10/08)
The reactivity of Os(2-MeC6H4)4 (1) toward Lewis bases has been studied. Reductive coupling in 1 on treatment with PMe3 or CO proceeds with σ- to π-rearrangement to the osmium(II) η6-biaryl derivatives, Os[η6-2-(2-MeC6H4)MeC6H 4](2-MeC6H4)2(L) (2, L = PMe3; 3, L = CO). Reaction of 1 with isocyanides yields two osmium(II) species: cis-Os(2-MeC6H4)2(CNR)4 (4a, R = t-Bu; 4b, R = 2,6-Me2C6H3) and fac-Os{C,N-3-Me[2-C(2-MeC6H4)NCMe3]C 6H3}(2-MeC6H4)(CNR)3 (5a, R = t-Bu; 5b R = 2,6-Me2C6H3). Treatment of 3 with excess t-BuNC gives cis,fac-Os(2-MeC6H4)2(t-BuNC)3(CO) (6). Compounds 2, 5a, and 6 have been crystallographically characterized. Crystal data with Mo Kα (λ = 0.71069 A?) radiation at 291 K are as follows. 2: monoclinic, space group P21/c, with a = 9.566 (2), b = 21.904 (3), c = 15.482 (5) A?, β = 96.67 (3)°, Z = 4, R = 0.0327 for 4149 observed data and 327 parameters. 5a: monoclinic, space group C2/C, with a = 36.882 (5), b = 13.885 (2), c = 18.337 (3) A?, β = 91.82 (1)°, Z = 8, R = 0.055 for 2423 observed data and 460 parameters. 6: monoclinic, space group P21/c, with a = 23.351 (5), b = 13.112 (4), c = 21.462 (7) A?, β = 108.40 (3)°, Z = 8 (two independent molecules), R = 0.069, for 4609 observed data and 291 parameters.
