The crystal structure of a pyridine-ligated, high-spin Ni(II) complex of 2,
3,7,8,12,13,17,18-octabromo-5,15-bis(isopropyl)-10,20-bis(isopropylidenyl)
porphyrin, 2, is reported and compared to the unligated, levy-spin Ni(II) c
omplex, 1, previously reported. The results demonstrate that conversion to
high-spin Ni(II) in nonplanar, sterically encumbered porphyrins induces a s
ignificant core expansion about the Ni while nonplanarity is still retained
. The expansion of the core parameters (Ni-N, Ct-C alpha, Ct-Cmeso) and the
Ni-N-axial distances are characteristic of the d(x2-y2) and d(z2) orbital
occupancies in high-spin Ni(II) porphyrins and document the structural cons
equences of the spin conversion in severely nonplanar NI(II) porphyrins. Th
e stereochemical results are particularly relevant to ligation effects in n
onplanar Ni biomolecules and synthetic porphyrins increasingly used as biom
imetic models of conformational effects in chromophores and prosthetic grou
ps in vivo, and to the remarkably wide range of lifetimes observed for exci
ted (d,d) states in nonplanar, sterically constrained Ni(II) porphyrins in
which the d(x2-y2) and d(z2) orbitals are also populated.