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

doi:10.1039/c1dt10788g

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 journal › Article › peer-review

18 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 language	English (US)
Pages (from-to)	10658-10663
Number of pages	6
Journal	Dalton Transactions
Volume	40
Issue number	40
DOIs	https://doi.org/10.1039/c1dt10788g
State	Published - Oct 28 2011

All Science Journal Classification (ASJC) codes

Inorganic Chemistry

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Alberding, B. G., Chisholm, M. H., Lear, B. J., Naseri, V., & Reed, C. R. (2011). 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. Dalton Transactions, 40(40), 10658-10663. https://doi.org/10.1039/c1dt10788g

Alberding, Brian G. ; Chisholm, Malcolm H. ; Lear, Benjamin James et al. / 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. In: Dalton Transactions. 2011 ; Vol. 40, No. 40. pp. 10658-10663.

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title = "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",

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.",

author = "Alberding, {Brian G.} and Chisholm, {Malcolm H.} and Lear, {Benjamin James} and Vesal Naseri and Reed, {Carly R.}",

year = "2011",

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language = "English (US)",

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Alberding, BG, Chisholm, MH, Lear, BJ, Naseri, V & Reed, CR 2011, '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', Dalton Transactions, vol. 40, no. 40, pp. 10658-10663. https://doi.org/10.1039/c1dt10788g

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. / Alberding, Brian G.; Chisholm, Malcolm H.; Lear, Benjamin James et al.
In: Dalton Transactions, Vol. 40, No. 40, 28.10.2011, p. 10658-10663.

Research output: Contribution to journal › Article › peer-review

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T1 - 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

AU - Alberding, Brian G.

AU - Chisholm, Malcolm H.

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AU - Naseri, Vesal

AU - Reed, Carly R.

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N2 - 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.

AB - 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.

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Alberding BG, Chisholm MH, Lear BJ, Naseri V, Reed CR. 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. Dalton Transactions. 2011 Oct 28;40(40):10658-10663. doi: 10.1039/c1dt10788g