Abstract  

Addition LiNHPh to a [(NacNac)Cr(μ-I)]₂ [NacNac = 2,4 pentane-N-N′-bis(2,6-diisopropylphenyl) ketiminato] in THF yields a dimeric anilido complex, 1, that crystallizes in P2₁/n with unit cell parameters a = 13.390(2) Å, b = 26.298(5) Å, c = 21.326(4) Å, β = 93.905(4)°, V = 7492(2) Å³ and Z = 4. The same reaction in the presence of aniline yields a monomeric anilido complex, 2, with a coordinated aniline molecule. Complex 2 crystallizes in P2 ₁ /c with unit cell parameters a = 28.530(5) Å, b = 10.8116(18) Å, c = 26.492(5) Å, β = 115.685(3)°, V = 7364(2) Å³ and Z = 8. Addition of aniline to isolated 1 yields 2. Addition of LiNPh₂ to [(NacNac)Cr(μ-I)]₂ in THF yields a monomeric complex that crystallizes in P2₁/n with the unit cell parameters a = 11.152(6) Å, b = 23.820(12) Å, c = 17.915(9) Å, β = 106.223(9)°, V = 4569(4) Å³ and Z = 4. All complexes have been spectroscopically and structurally characterized.

Graphical Abstract  

Addition of LiNHPh or LiNPh₂ to [(NacNac)Cr(μ-I)]₂ yields a dimeric or a monomeric complex whereas addition of LiNHPh in the presence of aniline yields the monomeric anilido complex.