Issue 40, 2011
From the journal:

Dalton Transactions

Synthesis and characterization of trans-M2(TiPB)2(O2C-CH[double bond, length as m-dash]CH-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 and L = π-accepting carboxylate ligand†

Brian G. Alberding,a   Malcolm H. Chisholm,*a   Benjamin J. Lear,a   Vesal Naseria  and  Carly R. Reeda  

* Corresponding authors

a Department of Chemistry, The Ohio State University, 100 W. 18th Ave, Columbus, OH, USA
E-mail: chisholm@chemistry.ohio-state.edu

Abstract

The preparation and characterization of the compounds trans-M2(TiPB)2(O2C-CH[double bond, length as m-dash]CH-2-C4H3S)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(TiPB)2L2 compounds where L = O2C-C6H4-4-CN, O2C-α,α′-terthienyl (TTh), and O2C-4-C6H4N-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 (S1) potential energy surfaces. These features are discussed in terms of the related electronic coupling of [M2]–[M2] complexes.

Graphical abstract: Synthesis and characterization of trans-M2(TiPB)2(O2C-CH [[double bond, length as m-dash]] CH-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 and L = π-accepting carboxylate ligand

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Article information

DOI
https://doi.org/10.1039/C1DT10788G
Article type
Paper
Submitted
28 Apr 2011
Accepted
23 Aug 2011
First published
20 Sep 2011

Dalton Trans., 2011,40, 10658-10663

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Synthesis and characterization of trans-M2(TiPB)2(O2C-CH[double bond, length as m-dash]CH-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 and L = π-accepting carboxylate ligand

B. G. Alberding, M. H. Chisholm, B. J. Lear, V. Naseri and C. R. Reed, Dalton Trans., 2011, 40, 10658 DOI: 10.1039/C1DT10788G

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