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- W1981930364 abstract "The differences in the geometries of Os(X)(CHR)(Cl)(CO)L2 (X=H, Cl; L=PPr3i; R=SiMe3, Ph), where X and CHR are mutually trans, have been studied through abinitio MP2 calculations (L=PH3, R=H). The optimized structures are in good agreement with the experimental data (P–Os–P=141.4° for X=H; 167.5° for X=Cl) and show the electronic origin of the distortion. A molecular orbital analysis explains why the P–Os–P angle is small for X=H and larger, but not 180°, for X=Cl. For X=H, the isomer in which H and CH2 are mutually cis is shown to be more stable than the corresponding experimental isomer in which they are mutually trans. However, the 16-electron product resulting from insertion of the carbene into the Os–H bond is shown to be considerably more stable than the 18-electron hydrido-carbene parent compound. Thus, the isolated metastable isomer is kinetically protected by a high barrier for site exchange in hexacoordinated complexes. Recent experimental observations by Caulton etal. have shown that Os(H)(CH2)(Cl)(CO)L2 transforms into Os(CH3)(Cl)(CO)L2 when the kinetic barrier is removed by loss of phosphine." @default.
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- W1981930364 date "1999-01-01" @default.
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- W1981930364 title "18-Electron Os(X)(CHR)(Cl)(CO)L2 (X=H, Cl): not octahedral and metastable?" @default.
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- W1981930364 doi "https://doi.org/10.1039/a809997i" @default.
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