MM Quadruply Bonded Complexes Supported by Vinylbenzoate Ligands: Synthesis, Characterization, Photophysical Properties and Application As Synthons

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2015 Sep 30

PMID 26417424

Authors

Samantha E Brown-Xu

Malcolm H Chisholm

Christopher B Durr

Thomas F Spilker

Philip J Young

Affiliations

Soon will be listed here.

Abstract

From the reactions between M(T PB) compounds and and - vinylbenzoic acids (2 equiv) in toluene at room temperature the compounds -M(T PB)L, where L = -vinylbenzoate (M = Mo) and (M = W) and T PB = 2,4,6-triisopropylbenzoate, and where L = -vinylbenzoate (M = Mo) and (M = W) have been isolated. Compounds and have been shown to undergo Heck carbon-carbon coupling reactions with phenyliodide to produce -Mo(T PB)(OCCH--CH=CH-CH) and -Mo(T PB)(OCCH--CH=CH-CH), . The molybdenum compounds and have been structurally characterized by single crystal X-ray crystallography. All the new compounds have been characterized by H NMR, IR, UV-Visible absorption and emission spectroscopy, high resolution MALDITOF MS, fs- and ns- transient absorption spectroscopy and fs- time-resolved IR spectroscopy. Electronic structure calculations employing density functional theory, DFT, and time-dependent DFT have been employed to aid in the interpretation of spectral data. All compounds show intense absorptions in the visible region corresponding to Mδ to Lπ* charge transfer transitions. The lifetimes of the MLCT state fall in the range of 1 - 10 ps and for the molybdenum complexes the T states are δδ* with lifetimes ~50 μs while for the tungsten complexes the T are MLCT with lifetimes in the range of 3 - 10 ns.

References

Barbara P, Gesquiere A, Park S, Lee Y . Single-molecule spectroscopy of conjugated polymers. Acc Chem Res. 2005; 38(7):602-10. DOI: 10.1021/ar040141w. View

Lee , Yang , PARR . Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B Condens Matter. 1988; 37(2):785-789. DOI: 10.1103/physrevb.37.785. View

Burdzinski G, Hackett J, Wang J, Gustafson T, Hadad C, Platz M . Early events in the photochemistry of aryl azides from femtosecond UV/Vis spectroscopy and quantum chemical calculations. J Am Chem Soc. 2006; 128(41):13402-11. DOI: 10.1021/ja061520i. View

Ren T . Peripheral covalent modification of inorganic and organometallic compounds through C-C bond formation reactions. Chem Rev. 2008; 108(10):4185-207. DOI: 10.1021/cr8002592. View

Burdzinski G, Chisholm M, Chou P, Chou Y, Feil F, Gallucci J . The remarkable influence of M2delta to thienyl pi conjugation in oligothiophenes incorporating MM quadruple bonds. Proc Natl Acad Sci U S A. 2008; 105(40):15247-52. PMC: 2563102. DOI: 10.1073/pnas.0807411105. View

Wang J, Burdzinski G, Kubicki J, Platz M . Ultrafast UV-vis and IR studies of p-biphenylyl acetyl and carbomethoxy carbenes. J Am Chem Soc. 2008; 130(33):11195-209. DOI: 10.1021/ja803096p. View

Brown-Xu S, Chisholm M, Durr C, Lewis S, Spilker T, Young P . Mo2 paddlewheel complexes functionalized with a single MLCT, S1 infrared-active carboxylate reporter ligand: preparation and studies of ground and photoexcited states. Inorg Chem. 2013; 53(1):637-44. DOI: 10.1021/ic402775s. View

Sheldrick G . A short history of SHELX. Acta Crystallogr A. 2007; 64(Pt 1):112-22. DOI: 10.1107/S0108767307043930. View

Alberding B, Chisholm M, Gallucci J, Ghosh Y, Gustafson T . Electron delocalization in the S1 and T1 metal-to-ligand charge transfer states of trans-substituted metal quadruply bonded complexes. Proc Natl Acad Sci U S A. 2011; 108(20):8152-6. PMC: 3100943. DOI: 10.1073/pnas.1103082108. View

10.

Brown-Xu S, Chisholm M, Durr C, Spilker T . Metal-metal quadruple bonds supported by 5-ethynylthiophene-2-carboxylato ligands: preparation, molecular and electronic structures, photoexcited state dynamics, and application as molecular synthons. J Am Chem Soc. 2013; 135(22):8254-9. DOI: 10.1021/ja400508u. View

11.

Alberding B, Chisholm M, Chou Y, Gallucci J, Ghosh Y, Gustafson T . Quadruply bonded dimetal units supported by 2,4,6-triisopropylbenzoates MM(TiPB)(4) (MM = Mo(2), MoW, and W(2)): preparation and photophysical properties. Inorg Chem. 2009; 48(10):4394-9. DOI: 10.1021/ic900092c. View

12.

Cotton F, Daniels L, Hillard E, Murillo C . Filling a void: isolation and characterization of tetracarboxylato dimolybdenum cations. Inorg Chem. 2002; 41(6):1639-44. DOI: 10.1021/ic011079r. View

13.

Alberding B, Chisholm M, Gustafson T . Detection of the singlet and triplet MM δδ* states in quadruply bonded dimetal tetracarboxylates (M = Mo, W) by time-resolved infrared spectroscopy. Inorg Chem. 2011; 51(1):491-8. DOI: 10.1021/ic201957a. View

14.

Byrnes M, Chisholm M, Gallucci J, Liu Y, Ramnauth R, Turro C . Observation of 1MLCT and 3MLCT excited states in quadruply bonded Mo2 and W2 complexes. J Am Chem Soc. 2005; 127(49):17343-52. DOI: 10.1021/ja055136h. View