Reactivity Differences of Pt0 Phosphine Complexes in C-C Bond Activation of Asymmetric Acetylenes
Reactivity Differences of Pt0 Phosphine Complexes in C-C Bond Activation of Asymmetric Acetylenes
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DOI：
10.1021/om900413a
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发表时间：
2009-11-23
期刊：
影响因子：
2.8
通讯作者：
Jones, William D.
中科院分区：
文献类型：
--
作者：
Gunay, Ahmet;Mueller, Christian;Jones, William D.
研究了不对称乙炔衍生物L2Pt（PhC CR）与1,2-二（二异丙基膦）乙烷（dippe）、1,2-二（二叔丁基膦）乙烷（dtpe）和1-二异丙基膦-2-二甲氨基乙胺（dippdmae）螯合物的碳-碳键活化反应。（dippe）Pt(eta(2)-PhC CCH3) （1a）、（dippe）Pt(eta(2)-PhC CCF3) （1b）和（dippe）Pt(eta(2)-PhC CC(CH3)(3)) （1c）在160℃下无热反应性，但1b在紫外光（>300 nm）照射下显示C-C裂解形成（dippe）Pt(Ph)（C CCF3）的证据。相比之下，这些金属配合物的dtpe类似物（dtpe）Pt(eta(2)-PhC CCH3) (2a), (dtpe)Pt(eta(2)-PhC CCF3) （2b）和（dtpe）Pt(eta(2)-PhC CC(CH3)(3)) （2c）在光解时显示C-H或C-C活化产物。2b生成（dtpe）Pt(Ph)(C - CCF3)，而2a或2c则通过活化C6D6溶剂生成（dtpe）Pt(D)(C6D5) （2D）。化合物2a-c在160℃下无热反应性，合成了两个与半可溶螯合物dippdmae的配合物，（dippdmae）Pt(eta(2)-PhC CCF3) （3b）和（dippdmae）Pt(eta(2)-PhC CC(CH3)(3)) （3c）。（L-2）Pt(Ph)（C - CCF3）型C-C裂解产物仅在化合物1b、2b和3b光解时观察到。
Carbon-carbon bond activation reactions of asymmetric acetylene derivatives of the type L2Pt(PhC CR) were studied with 1,2-bis(diisopropylphosphino)ethane (dippe), 1,2-bis(di-tert-butylphosphino)ethane (dtbpe), and 1-diisopropylphosphino-2-dimethylaminoethine (dippdmae) chelates. (dippe)Pt(eta(2)-PhC CCH3) (1a), (dippe)Pt(eta(2)-PhC CCF3) (1b), and (dippe)Pt(eta(2)-PhC CC(CH3)(3)) (1c) showed no thermal reactivity at 160 degrees C, but 1b showed evidence for C-C cleavage to form (dippe)Pt(Ph)(C CCF3) upon irradiation with UV light (>300 nm). In comparison, dtbpe analogues of these metal complexes, (dtbpe)Pt(eta(2)-PhC CCH3) (2a), (dtbpe)pt(eta(2)-phC CCF3) (2b), and (dtbpe)Pt(eta(2)-PhC CC(CH3)(3)) (2c), showed either C-H or C-C activation products upon photolysis. 2b produced (dtbpe)Pt(Ph)(C CCF3), but 2a or 2c showed the formation of (dtbpe)Pt(D)(C6D5) (2D) by activation of the C6D6 solvent. Compounds 2a-c showed no thermal reactivity at 160 degrees C. Two complexes with the hemilabile chelate dippdmae were synthesized and fully characterized, (dippdmae)Pt(eta(2)-PhC CCF3) (3b) and (dippdmae)Pt(eta(2)-PhC CC(CH3)(3)) (3c). C-C cleavage products of the type (L-2)Pt(Ph)(C CCF3) were observed only upon photolysis of compounds 1b, 2b, and 3b.