Models for aerobic carbon monoxide dehydrogenase: synthesis characterization and reactivity of paramagnetic MoVO(μ-S)CuI complexes

摘要

Reaction of [CoCp2][Tp^iPrMoOS(OAr)] [Cp = η⁵-cyclopentadienyl; Tp^iPr = hydrotris(3-isopropylpyrazol-1-yl)borate; OAr = phenolate or derivative thereof] with [Cu(NCMe)(Me3tcn)]BF4 (Me3tcn = 1,4,7-trimethyl-1,4,7-triazacyclononane) in MeCN at –30 °C results in the formation of red-brown/black, paramagnetic, μ-sulfido-Mo(v)/Cu(i) complexes, Tp^iPrMoO(OAr)(μ-S)Cu(Me3tcn). The complexes possess the MoO(μ-S)Cu core found in aerobic carbon monoxide dehydrogenases (CODHs) and exhibit X-band EPR spectra closely related to those of semi-reduced CODH, with giso ∼ 1.937, hyperfine coupling to ^95,97Mo (aiso = 39–42 × 10^–4 cm^–1) and strong superhyperfine coupling to ^63,65Cu (aiso = 34–63 × 10^–4 cm^–1). Anisotropic spectra exhibit monoclinic symmetry with g1 ∼ 1.996, g2 ∼ 1.944 and g3 ∼ 1.882, and nearly isotropic ACu values (75–90 × 10^–4 cm^–1). The X-ray structures of four derivatives (Ar = Ph, C6H4^tBu-2, C6H4^sBu-2, C₆H₄Ph-4) are reported and discussed along with that of the Ar = C₆H₃^tBu₂-3,5 derivative (communicated in C. Gourlay, D. J. Nielsen, J. M. White, S. Z. Knottenbelt, M. L. Kirk and C. G. Young, J. Am. Chem. Soc., 2006, >128, 2164). The complexes exhibit distorted octahedral oxo-Mo(v) and distorted tetrahedral Cu(i) centres bridged by a single bent μ-sulfido ligand, with Mo–S and Cu–S distances and Mo–S–Cu angles in the ranges 2.262–2.300 Å, 2.111–2.134 Å and 115.87–134.27°, respectively. The 2 t-butyl derivative adopts a unique phenolate conformation with OMo–O–Cα and OMo–S–Cu torsion angles of 92.7 and 21.1°, respectively, very different from those of the other structurally characterized derivatives (31–47 and 33–45°, respectively) and exhibits a relatively short Mo···Cu distance [3.752(2) Å vs. 3.806(7)–4.040(2) Å]. As well, the a_Cu value of this complex (34.3 × 10^–4 cm^–1) is much lower than the values observed for other members of the series (55–63 × 10^–4 cm^–1), supporting the hypothesis that the electronic structure of the MoO(μ-S)Cu core unit and the degree of intermetallic communication are strongly dependent on the geometry of the MoO(OR)(μ-S)Cu unit. The complexes participate in an electrochemically reversible Mo(vi)/Mo(v) redox couple and react with cyanide undergoing decupration and desulfurization reactions of the type observed for CODH.