163557-08-2Relevant academic research and scientific papers
Generation of (2,3-η)-naphthalyne-nickel(0) complexes and their reactions with unsaturated molecules
Bennett, Martin A.,Hockless, David C. R.,Wenger, Eric
, p. 2091 - 2101 (2008/10/09)
Sodium-amalgam reduction of the (3-bromonaphthyl)nickel(II) complexes NiBr(3-Br-2-C10H6)L2 gives the first monomeric nickel(0) complexes of 2,3-naphthalyne, Ni(η2-C10H6)L2 (2L = 2 PEt3 (2), dcpe (5); dcpe = 1,2-bis(dicyclohexylphosphino)ethane, Cy2PCH2CH2PCy2). Complex 2 undergoes double-insertion reactions with dimethyl acetylenedicarboxylate (DMAD) or diphenylacetylene to give 1,2,3,4-tetrasubstituted anthracenes, C14H6R4 (R = CO2Me (8), Ph (9)). Complex 5 reacts with CO2 and with C2F4 to give isolable products of monoinsertion into the naphthalyne-nickel(0) bond, Ni(3-C10H6COO-2)(dcpe) (6) and Ni(3-C10H6CF2CF2-2)(dcpe) (7), respectively, and 7 undergoes further insertion with DMAD to give Ni{3-C(CO2Me)=C(CO2Me)C10H6CF 2CF2-2}(dcpe) (10). The structures of 6, 7, and 10 have been solved by heavy-atom methods and refined by least-squares methods. Crystal data: 6, space group P21/n (No. 14), a = 14.714(2) A?, b = 17.100(1) A?, c = 15.990(2) A?, β = 110.244(9)°, Z = 4, 2997 observed reflections (I > 3σ(I)) with R = 4.1 and Rw = 2.8; 7, space group P21/c (No. 14), a = 11.139(2) A?, b = 19.557(2) A?, c = 16.809(2) A?, β = 92.927(9)°, Z = 4, 3872 observed reflections (7 > 3σ(I)) with R = 3.5 and Rw = 2.9; 10, space group P1 (No. 2), a = 9.415(3) A?, b = 11.759(2) A?, c = 20.218(3) A?, α = 93.94(1)°, β = 94.77(2)°, γ = 108.90-(2)°, Z = 2, 4432 observed reflections (I > 3σ(I)) with R = 3.6 and Rw = 3.0.
