Synthesis and Reactivity of Molybdenum Complexes Containing Functionalized Alkynyl Ligands: A Photochemically Activated CO-Releasing Molecule (PhotoCO-RM)
Synthesis and Reactivity of Molybdenum Complexes Containing Functionalized Alkynyl Ligands: A Photochemically Activated CO-Releasing Molecule (PhotoCO-RM)
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DOI：
10.1021/om200495h
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发表时间：
2011-09-12
期刊：
影响因子：
2.8
通讯作者：
Lynam, Jason M.
中科院分区：
文献类型：
--
作者：
Zhang, Wei-Qiang;Atkin, Anthony J.;Lynam, Jason M.
[MoCl(ETA(5)-C5H5)(CO)(3)]与丙烯醇Hez(CCRROH)-R-1-O-2在催化量CuI存在下，以NEt2H为溶剂反应生成[Mo(C(CCRROH)-R-1-O-2)(ETA(5)-C5H5)(CO)(3)]。用单晶X-射线衍射法确定了R-1=R-2=Me和R-1=Me，R-2=Ph的结构。该方法可以推广到一系列的炔丙基醚和炔丙基酯，从而可以制备含有侧基水杨酸基和β-D-果糖基团的钼配合物。烯丙基配合物[Mo(C-CCH_2OH)(eta(5)-C_5H_5)(CO)(3)]与NEt2H进一步反应，得到取代的烯丙基络合物[Mo(eta(3)-H2CC{NEt2}CHC{O}NEt2)(eta(5)-C5H5)(CO)(3)].在CuI存在下，以吡咯烷或哌啶为溶剂，[MoCl(ETA(5)-C5H5)(CO)(3)]与HC-CCH_2OH反应可得到类似的产物。在与哌啶反应的情况下，可以分离出另一个产物，该产物是由两个丙炔醇分子偶联而得到丁二烯配体的。研究了其中一些新型络合物的CO释放性能。在含有β-D-果糖吡喃糖基的水溶性炔基化合物中，CO的释放被紫外光促进，揭示了一类新的光化学激活的CO释放分子(PhotoCO-RMS)。
Reaction of [MoCl(eta(5)-C5H5)(CO)(3)] with propargyl alcohols Hez (CCRROH)-R-1-O-2 in the presence of catalytic amounts of CuI and using NEt2H as solvent results in the formation of alkynyl complexes [Mo(C (CCRROH)-R-1-O-2)(eta(5)-C5H5)(CO)(3)]. The structure of the complexes where R-1 = R-2 = Me and R-1 = Me, R-2 = Ph were confirmed by single-crystal X-ray diffraction. The method could be extended to a range of propargyl ethers and propargyl esters, which allowed for the preparation of molybdenum complexes containing pendant salicylate and beta-D-fructopyranose groups. The alkynyl complex [Mo(C CCH2OH)(eta(5)-C5H5)(CO)(3)] undergoes a further reaction with NEt2H to give the substituted allyl complex [Mo(eta(3)-H2CC{NEt2}CHC{O}NEt2)(eta(5)-C5H5)(CO)(3)]. Similar products could be obtained from the reaction of [MoCl(eta(5)-C5H5)(CO)(3)] with HC CCH2OH in the presence of CuI using pyrrolidine or piperidine as solvent. In the case of the reaction with piperidine a further product could be isolated that has arisen from the coupling of two propargyl alcohol molecules to afford a butadienyl ligand. The CO-releasing properties of a number of these novel complexes have been investigated. In the case of the water-soluble alkynyl complex containing a beta-D-fructopyranose group CO release was shown to be promoted by exposure to UV light, revealing a new class of photochemically activated CO-releasing molecules (PhotoCO-RMs).