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首页> 外文期刊>Chemical science >Models for aerobic carbon monoxide dehydrogenase: synthesis, characterization and reactivity of paramagnetic MoVO(μ-S)CuI complexes
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Models for aerobic carbon monoxide dehydrogenase: synthesis, characterization and reactivity of paramagnetic MoVO(μ-S)CuI complexes

机译：好氧一氧化碳脱氢酶模型：顺磁性Mo V O（μ-S）Cu I 配合物的合成，表征和反应性

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Reaction of [CoCp2][TpiPrMoOS(OAr)] [Cp = η5-cyclopentadienyl; TpiPr = 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, TpiPrMoO(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, C6H4tBu-2, C6H4sBu-2, C6H4Ph-4) are reported and discussed along with that of the Ar = C6H3tBu2-3,5 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 ?, 2.111–2.134 ? 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) ? vs. 3.806(7)–4.040(2) ?]. As well, the aCu 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.
机译：[CoCp 2 ] [Tp iPr MoOS（OAr）]的反应[Cp =η < sup> 5 -环戊二烯基; Tp iPr =氢化三（3-异丙基吡唑-1-基）硼酸酯; OAr =酚盐或其衍生物]与[Cu（NCMe）（Me 3 tcn）] BF 4 （ MeCN在30°C下的Me 3 tcn = 1,4,7-三甲基-1,4,7-三氮杂环壬烷）形成红棕色/黑色，顺磁性，μ-硫化物-Mo（ V ）/ Cu（ I ）配合物，Tp iPr MoO （OAr）（μ-S）Cu（Me 3 tcn）。该复合物具有在好氧一氧化碳脱氢酶（CODH）中发现的MoO（μ-S）Cu核，并显示与半还原CODH密切相关的X波段EPR光谱， g iso 〜1.937，与 95,97 Mo（ a iso = 39–42×10 ？4 cm ？1 ）和与 63,65 Cu（ a iso = 34– 63×10 ？4 cm ？1 ）。各向异性光谱表现出 g 1 〜1.996， g 2 的单斜对称性> 〜1.944和 g 3 〜1.882，以及几乎各向同性的 A Cu 值（75–90×10 ？4 cm ？1 ）。四个导数（Ar = Ph，C 6 H 4 t Bu-2，C 6 H 4 < / small> s Bu-2，C 6 H 4 Ph-4）与Ar = C 6 H 3 t Bu 2 -3,5导数（在C. Gourlay中进行通信，DJ Nielsen，JM White，SZ Knottenbelt，ML Kirk和CG Young， J。Am。Chem。Soc。，2006，128，2164）。配合物表现出扭曲的八面体氧-Mo（ V ）和扭曲的四面体Cu（ I ）中心，这些中心由单个弯曲的μ-硫键配体桥接，Mo–S和Cu– S距离和Mo–S–Cu角在2.262–2.300？，2.111–2.134？范围内。和115.87–134.27°。 2 t -丁基衍生物采用独特的酚酸酯构型，其OMo–O–Cα和OMo–S–Cu扭转角分别为92.7和21.1°，与其他结构表征的衍生物的扭转角非常不同（分别为31-47和33-45°），并且Mo？Cu距离相对较短[3.752（2）？ vs。 3.806（7）–4.040（2）吗？]。同样，该复合物的 a Cu 值（34.3×10 ？4 cm ？1 ）比该系列其他成员（55–63×10 ？4 ）观察到的值低得多 cm ？1 ），支持以下假设：MoO（μ-S）Cu核单元的电子结构和金属间的连通程度强烈依赖MoO（OR）（μ-S）Cu单元的几何形状配合物参与电化学可逆的Mo（ VI ）/ Mo（ V ）氧化还原对，并与氰化物发生反应，并经历CODH观察到的衰耗和脱硫反应。

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