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- W2018935596 abstract "The complex Os(dmpe)2H2 (dmpe = Me2PCH2CH2PMe2) was synthesized by reaction of trans-Os(dmpe)2Cl2 with sodium under hydrogen and was shown to consist of cis and trans isomers in a ratio of ca. 60:1. UV irradiation in argon and methane matrices yielded Os(dmpe)2 with a characteristic multiband UV−vis spectrum; the lowest energy transition occurs close to 800 nm. In CO-doped matrices, Os(dmpe)2(CO) was generated. Laser flash photolysis experiments (266 nm excitation) demonstrated that the same species was produced in cyclohexane solutions of Os(dmpe)2H2 at room temperature. The initial photoproduct, Os(dmpe)2, is formed within 60 ns of the laser flash. This species reacts with hydrogen and with CO with rate constants exceeding 109 dm3 mol-1 s-1, indicating that there is essentially no barrier to its reaction with these substrates. Rate constants for reaction with ethene, triethylsilane, and nitrogen are all close to 108 dm3 mol-1 s-1. Comparison of the UV−vis spectrum of Os(dmpe)2 with Ru0, Rh+, and Ir+ analogues indicates that Os(dmpe)2 has a structure close to square planar (local D2h symmetry). The products of photochemical reaction of Os(dmpe)2H2 in solution were also studied by NMR spectroscopy. Reaction with benzene yields cis-Os(dmpe)2(Ph)H, while reaction with ethene yields cis- and trans-Os(dmpe)2(CHCH2)H." @default.
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- W2018935596 title "Photochemistry of Os(dmpe)<sub>2</sub>H<sub>2</sub>: Matrix, Transient Solution, and NMR Studies of 16-Electron Os(dmpe)<sub>2</sub> (dmpe = Me<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>PMe<sub>2</sub>)" @default.
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- W2018935596 doi "https://doi.org/10.1021/om9806141" @default.
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