π-酸/π-碱羰基氧钼（IV）配合物及其氧钼（VI/IV）前体。
Pi-acid/pi-base carbonyloxomolybdenum(IV) complexes and their oxomolybdenum(VI/IV) precursors.
作者信息
Malarek Michael S, Evans David J, Smith Paul D, Bleeker Ashley R, White Jonathan M, Young Charles G
机构信息
School of Chemistry, University of Melbourne, Victoria 3010, Australia.
出版信息
Inorg Chem. 2006 Mar 6;45(5):2209-16. doi: 10.1021/ic0510314.
Brown TpiPrMoO(SR)(CO) (TpiPr = hydrotris(3-isopropylpyrazol-1-yl)borate; R = Et, iPr, Ph, p-tol, Bz) are formed when TpiPrMoO(SR)(NCMe) react with CO gas in toluene. The carbonyloxomolybdenum(IV) complexes exhibit nu(CO) and nu(Mo=O) IR bands at ca. 2025 and 935 cm(-1), respectively, and NMR spectra indicative of C(1) symmetry, with delta(C)(CO) ca. 250. The crystal structure of TpiPrMoO(SiPr)(CO), the first for a mononuclear carbonyloxomolybdenum complex, revealed a distorted octahedral geometry, with d(Mo=O) = 1.683(3) A, d(Mo-C) = 2.043(5) A, and angle(O=Mo-C) = 90.87(16) degrees . The blue-green acetonitrile precursors are generated by reacting cis-TpiPrMoO2(SR) with PPh3; they are unstable, display a single nu(Mo=O) IR band at ca. 950 cm(-1), and exhibit NMR spectra consistent with C1 symmetry. Red-brown cis-TpiPrMoO2(SR) (R = as above and tBu) are formed by metathesis of TpiPrMoO2Cl and HSR/NEt3 in dichloromethane. The complexes exhibit strong nu(MoO2) IR bands at ca. 925 and 895 cm(-1), and NMR spectra indicative of Cs symmetry; the isopropyl, p-tolyl, and benzyl derivatives possess distorted octahedral geometries, with d(Mo=O)(av) = 1.698 A and angle(MoO(2))(av) = 103.5 degrees.
当三（3 - 异丙基吡唑 - 1 - 基）硼酸氢钼（TpiPrMoO(SR)(NCMe)）与一氧化碳气体在甲苯中反应时，会生成Brown TpiPrMoO(SR)(CO)（TpiPr = 三（3 - 异丙基吡唑 - 1 - 基）硼酸根；R = 乙基、异丙基、苯基、对甲苯基、苄基）。羰基氧钼（IV）配合物在约2025和935 cm⁻¹处分别显示出ν(CO)和ν(Mo=O)红外吸收带，并且核磁共振谱表明具有C₁对称性，δ(C)(CO)约为250。单核羰基氧钼配合物中首个配合物TpiPrMoO(SiPr)(CO)的晶体结构显示出扭曲的八面体几何构型，d(Mo=O) = 1.683(3) Å，d(Mo - C) = 2.043(5) Å，以及∠(O=Mo - C) = 90.87(16)°。蓝绿色的乙腈前体是通过顺式 - TpiPrMoO₂(SR)与三苯基膦反应生成的；它们不稳定，在约950 cm⁻¹处显示出单个ν(Mo=O)红外吸收带，并且核磁共振谱与C₁对称性一致。红棕色的顺式 - TpiPrMoO₂(SR)（R = 上述基团以及叔丁基）是通过在二氯甲烷中使TpiPrMoO₂Cl与HSR/三乙胺进行复分解反应形成的。这些配合物在约925和895 cm⁻¹处显示出强的ν(MoO₂)红外吸收带，并且核磁共振谱表明具有Cs对称性；异丙基、对甲苯基和苄基衍生物具有扭曲的八面体几何构型，d(Mo=O)(平均) = 1.698 Å，∠(MoO₂)(平均) = 103.5°。
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