✍ Scribed by Tanya M Ramond; Gustavo E Davico; Fredrik Hellberg; Fredrik Svedberg; Peter Salén; Patrick Söderqvist; W.Carl Lineberger
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The 364-nm negative ion photoelectron spectra of XO and OXO molecules (X = Ni, Pd, and Pt) are reported. The spectra yield the electron affinities (EAs): EA(NiO) = 1.455 ± 0.005 eV; EA(PdO) = 1.672 ± 0.005 eV; EA(PtO) = 2.172 ± 0.005 eV; EA(ONiO) = 3.043 ± 0.005 eV; EA(OPdO) = 3.086 ± 0.005 eV; EA(OPtO) = 2.677 ± 0.005 eV. In addition, for the diatomics, transitions from the anion X 2 3/2 and X 2 1/2 states into neutral X 3 -, 3 , and for NiO and PdO, 1 , are assigned. Several states have been reassigned from those in the existing literature. Anion 2 3/2 -2 1/2 spin-orbit splittings are measured, as are neutral 3 2 -3 1 spin-orbit splittings: the XO 3 2 -3 1 splittings increase from 405 ± 30 cm -1 (NiO) to 805 ± 30 cm -1 (PdO) to 3580 ± 40 cm -1 (PtO). A bond length shortening of 0.03 ± 0.01 Å is measured upon electron detachment from NiO -, resulting in an anion bond length of 1.66 ± 0.01 Å. The bond length does not change upon electron detachment from PdO -using 3.4-eV photons. The Pt-O bond length decreases by 0.035 ± 0.010 Å in the 3 1 ← 2 3/2 transition. The spectrum of OPtO displays a significantly more extended vibrational progression than those of ONiO or OPdO, and the O-Pt bond length is found to decrease by 0.07 ± 0.01 Å upon electron detachment. The spectra support the view that the Ni-O bond is largely ionic, the Pd-O bond is somewhat less so, and the Pt-O bond displays a substantial covalent character.
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gave a value of 297. (The preparation of (CH3CN)3Cr(C0)3 was as described by Tare [41.) Reaction conditions: stirring at 30 "C and 1 5 mm/Hg for some hours. Table 1. Comparison of tricarbonylhexamethyiborazolechromiurn with a typical rr-complex and a Lewis-base complex Appearance Behaviour in high v