Synthesis and characterization of trans-M2(TiPB) 2(O2C-CHCH-2-C4H3S)2 (M = Mo or W) and comments on the metal-to-ligand charge transfer bands in MM quadruply bonded complexes of the type trans-M2(TiPB) 2L2, where TiPB = 2,4,6-triisopropylbenzoate

Brian G. Alberding, Malcolm H. Chisholm, Benjamin James Lear, Vesal Naseri, Carly R. Reed

Research output: Contribution to journalArticle

17 Scopus citations

Abstract

The preparation and characterization of the compounds trans-M 2(TiPB)2(O2C-CHCH-2-C 4H3S)2 where M = Mo or W and TiPB = 2,4,6-triisopropylbenzoate are reported. The optical spectra of the new compounds are compared with those of related trans-M2(T iPB)2L2 compounds where L = O 2C-C6H4-4-CN, O2C-α, α′-terthienyl (TTh), and O2C-4-C6H 4N-B(C6F5)3, that show strong metal-to-ligand charge transfer bands because of M2δ to Lπ conjugation, and are notably temperature dependant due to the various conformations of the two trans-L groups. Upon cooling the spectral features sharpen as the planar geometry that optimizes M2δ-Lπ conjugation is favored. As the electronic coupling of the two trans-Lπ systems increases the (0,0) electronic transition gains intensity indicating a greater nesting of the ground state (S0) and excited state (S 1) potential energy surfaces. These features are discussed in terms of the related electronic coupling of [M2]-[M2] complexes.

Original languageEnglish (US)
Pages (from-to)10658-10663
Number of pages6
JournalDalton Transactions
Volume40
Issue number40
DOIs
StatePublished - Oct 28 2011

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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