Models for the molybdenum hydroxylases: Synthesis, characterization and reactivity of cis-oxosulfido-Mo(VI) complexes

Abstract

Atom transfer reactions have been employed to convert Tp iPrMoO2(OAr) into monomeric cisoxosulfido-Mo(VI) and dlmeric μ-disulfido-Mo(V) species, [TpiPrMoOS(OAr)]n (Tp iPr = hydrotris(3-Isopropylpyrazol-1-yl)borate: OAr = phenolate or naphtholate derivative; n = 1 and 2, respectively). Dark red, monomeric Tp iPrMoOS(OAr) complexes contain distorted octahedral cis-oxosulfido-Mo(VI) centers, with d(Mo=O) = 1.692(5) A, d(Mo=S) = 2.132(2) Å, and Z(O=Mo=S) = 103.68(16)° for the 2-sec-butylphenolate derivative. Dark red-purple, dimeric [TpiPrMoOS(OAr)]2 complexes undergo S-S bond cleavage forming monomeric oxosulfido-Mo(VI) species in solution. In the solid state, the 3,5-di-tertbutylphenolate deri..