Extremely bulky amido first row transition metal(II) halide complexes: potential precursors to low coordinate metal-metal bonded systems.

Reactions of the extremely bulky potassium amide complexes, [KL'(η(6)-toluene)] or [KL"] (L'/L" = N(Ar*)(SiR3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4; R = Me (L') or Ph (L")), with a series of first row transition metal(II) halides have yielded 10 rare examples of monodentate amido first row transition metal(II) halide complexes, all of which were crystallographically characterized. They encompass the dimeric, square-planar chromium complexes, [{CrL'(THF)(μ-Cl)}2] and [{CrL"(μ-Cl)}2], the latter of which displays intramolecular η(2)-Ph···Cr interactions; the dimeric tetrahedral complexes, [{ML'(THF)(μ-Br)}2] (M = Mn or Fe), [{ML"(THF)(μ-X)}2] (M = Mn, Fe or Co; X = Cl or Br) and [{CoL"(μ-Cl)}2] (which displays intramolecular η(2)-Ph···Co interactions); and the monomeric zinc amides, [L'ZnBr(THF)] (three-coordinate) and [L"ZnBr] (two-coordinate). Solution state magnetic moment determinations on all but one of the paramagnetic compounds show them to be high-spin systems. Throughout, comparisons are made with related bulky terphenyl transition metal(II) halide complexes, and the potential for the use of the prepared complexes as precursors to low-valent transition metal systems is discussed.