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Structural Basis for Unusually Long Wavelength Charge Transfer Transitions in Complexes MCl(ECH2CH2NMe2)(PR3) (E = Te, Se; M = Pt, Pd): Experimental Results and TD-DFT Calculations

, , , , , und . Inorganic Chemistry 41 (11): 2864--2870 (2002)

Zusammenfassung

The new blue complexes, PdCl(TeCH2CH2NMe2)(PR3) (PR3 = PEt3, PPr3, PBu3, PMe2Ph, PMePh2, PPh3, PTol3) and the red PtCl(TeCH2CH2NMe2)(PR3) (PR3 = PMe2Ph, PMePh2), were synthesized and studied spectroscopically (1H and 31P NMR, UV/visible) and by cyclic voltammetry. The structures of PdCl(TeCH2CH2NMe2)(PPr3) (2b) PdCl(TeCH2CH2NMe2)(PMePh2) (2e), PtCl(TeCH2CH2NMe2)(PMePh2) (2i), and the related PtCl(SeCH2CH2NMe2)(PEt3) (3) were detd. crystallog., revealing a typical pattern of trans-positioned neutral N and P donor atoms in an approx. square planar setting. The mols. 2b, 2e, and 2i were calcd. by TD-DFT methodol. to understand the origin of the weak (e $\approx$ 200 M-1 cm-1) long-wavelength bands at $\sim$600 nm for Pd/Te complexes such as 2b or 2e, at $\sim$460 nm for Pt/Te systems such as 2i, and at $\sim$405 nm for Pt/Se analogs such as 3. These transitions are identified as charge transfer transitions from the selenolato or tellurolato centers to unoccupied orbitals involving mainly the phosphine coligands for the PtII compds. and more delocalized MOs for the PdII analogs. Calcns. and electrochem. data were used to rationalize the effects of metal and chalcogen variation. on SciFinder(R)

Links und Ressourcen

DOI:
10.1021/ic011210v
BibTeX-Schlüssel:
Dey.2002
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