Photochemistry of low-valent platinum metal complexes and application to photocatalytic systems

配合物的合成。合成了[M（triphos）（PPh_3）]、[M（binap）_2]（M=Pt和Pd），并通过元素分析和NMR进行了表征。（triphos = 1，1，1-三（二苯基膦基甲基）乙烷，binap = 1，1 ′-双（二苯基膦基）-2，2 ′-联萘）。[Pd（triphos）（PPh_3）]的发光呈双指数衰减。在激发态的动力学进行了彻底的检查。光化学与氧。在[Pt（binap）_2]与氧的光化学反应的初始阶段，有单线态氧的生成。构建了一个简单的红外光探测系统，成功地探测到了单线态氧发射的1270 nm光。单重态氧的形成可能是通过能量传递机制。配合物与醇的光化学反应。研究了钯、铂配合物与乙醇的光化学反应。以汞灯为光源，用气相色谱仪鉴定产物中的有机物。乙醛的生成量是配合物催化的8倍以上。配合物与有机卤化物的光化学反应。[M（triphos）（PPh_3）]（或[M（binap）_2]）与1，2-二氯乙烷的溶液在可见光照射下，迅速定量产生乙烯。此外，还研究了以甲醇钾为催化剂，[Pd（triphos）（PPh_3）]催化二氯乙烷和氯苯的光化学脱卤反应。

Synthesis of the complexes. [M(triphos)(PPh_3)], [M(binap)_2] (M=Pt and Pd) were synthesized and characterized by elemental analyses and NMR spectroscopy. (triphos = 1,1,1 -tris(diphenylphosphinomethyl)ethane, binap = 1,1' -bis(diphenyl-phosphino)-2,2' -binaphthyl).Analyses of the excited states. The luminescence of [Pd(triphos)(PPh_3)] shows a biexponential decay. The dynamics in the excited state was thoroughly examined.Photochemistry with oxygen. Formation of singlet oxygen is suggested in the initial stage of the photochemical reaction of [Pt(binap)_2] and oxygen. A simple infrared light detection system was constructed, and 1270 nm-light of the emission from singlet oxygen was successfully detected. The singlet oxygen may be formed via an energy-transfer mechanism.Photochemical reaction of the complexes with alcohol. The photochemical reactions of the Pd and Pt complexes with ethanol were, studied. A mercury lamp was used as a light source and, a gas chromatograph was used to identify the organic product in the products. The amounts of the produced acetaldehyde were up to 8 times that of the complex used as a catalyst.Photochemical reaction of the complexes with organic halides. The solution of [M(triphos)(PPh_3)] (or [M(binap)_2]) and 1,2-dichloroethane was irradiated with visible light promptly yielded ethylene quantitatively. In addition, the photochemical dehalogenation of dichloroethane and chlorobenzene by [Pd(triphos) (PPh_3)] catalyst was confirmed with a use of potassium methoxide.