Structural studies and matrix photochemistry of tetramethyloxorhenium(VI), (CH3)4ReO, and related compounds

摘要: The crystal structure of tetramethyloxorhenium(VI), (CH3)4ReO, 1, at 150 K reveals molecules with a square-based pyramidal skeleton and dimensions very similar to those in the gas phase. related binuclear compound [(CH3)3Re(O)]2O, 2, has likewise been shown feature rhenium centres coordination geometry linked by linear Re–O–Re bridge carrying terminal ReO bonds that are mutually trans. Salient average (distances A, angles °) as follows: 1 Re–C 2.110(8), 1.684(4), ORe–C 112.6(2), C–Re–C 81.5(5) 134.8(3); 2 2.095–2.134(11), 1.675(6), Re–O 1.851(1), 103.0–113.5(4), C–Re–C 79.2(4) 132.5–137.0(4). Density functional theory (DFT) calculations have performed predict ionization energies for (CH3)4ReO. In light these results, photoelectron spectrum reassigned. IR spectroscopic measurements used chart reactions activated irradiating solid argon matrices doped broad-band UV-visible (200 ≤ λ ≤ 800 nm). spectra interpreted on basis additional experiments (CD3)4ReO, 1-d12, comparison either vibrational properties forecast or known molecules. Hence photoexcitation is result elimination methane formation novel methylidene–rhenium(VI) H2CRe(O)(CH3)2, 3. results discussed relation photochemistry methyltrioxorhenium(VII) circumstances.