Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange

Kenneth J.H. Young; Kapil S. Lokare; Chin Hin Leung; Mu Jeng Cheng; Robert J. Nielsen; Nicos A. Petasis; William A. Goddard; Roy A. Periana

doi:10.1016/j.molcata.2011.01.029

Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange

Kenneth J.H. Young
, Kapil S. Lokare
, Chin Hin Leung
, Mu Jeng Cheng
, Robert J. Nielsen
, Nicos A. Petasis
, William A. Goddard
, Roy A. Periana

University of Southern California
Scripps Florida
California Institute of Technology

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

15 Citations (Scopus)

Abstract

Using tridentate, neutral PyBox ligands, several new osmium and ruthenium complexes [M(PyBox)Cl₂(C₂H₄), where M = Ru, Os] have been prepared, all thermally stable. Some of these PyBox compounds are active for C-H activation of benzene. The Os(PyBox)Cl₂(C ₂H₄) complex was characterized by X-ray diffraction. DFT calculations (B3LYP and M06 including Poisson-Boltzmann solvation) corroborate that the Os/PyBox complex in acetic acid (ΔG^‡ = 32.0 kcal/mol) is more reactive for benzene C-H activation than Ru/PyBox in basic conditions (ΔG^‡ = 34.8 kcal/mol at pH = 13). The stability of hydroxide- and chloride-bridged dinuclear resting states determines calculated barriers.

Original language	English
Pages (from-to)	17-23
Number of pages	7
Journal	Journal of Molecular Catalysis A: Chemical
Volume	339
Issue number	1-2
DOIs	https://doi.org/10.1016/j.molcata.2011.01.029
Publication status	Published - 1 Apr 2011
Externally published	Yes

Keywords

C-H activation
Osmium
PyBox
Ruthenium

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10.1016/j.molcata.2011.01.029

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Young, K. J. H., Lokare, K. S., Leung, C. H., Cheng, M. J., Nielsen, R. J., Petasis, N. A., Goddard, W. A., & Periana, R. A. (2011). Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange. Journal of Molecular Catalysis A: Chemical, 339(1-2), 17-23. https://doi.org/10.1016/j.molcata.2011.01.029

@article{efbf2b875c514e6d97722720c9d7bbad,

title = "Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange",

abstract = "Using tridentate, neutral PyBox ligands, several new osmium and ruthenium complexes [M(PyBox)Cl2(C2H4), where M = Ru, Os] have been prepared, all thermally stable. Some of these PyBox compounds are active for C-H activation of benzene. The Os(PyBox)Cl2(C 2H4) complex was characterized by X-ray diffraction. DFT calculations (B3LYP and M06 including Poisson-Boltzmann solvation) corroborate that the Os/PyBox complex in acetic acid (ΔG‡ = 32.0 kcal/mol) is more reactive for benzene C-H activation than Ru/PyBox in basic conditions (ΔG‡ = 34.8 kcal/mol at pH = 13). The stability of hydroxide- and chloride-bridged dinuclear resting states determines calculated barriers.",

keywords = "C-H activation, Osmium, PyBox, Ruthenium",

author = "Young, \{Kenneth J.H.\} and Lokare, \{Kapil S.\} and Leung, \{Chin Hin\} and Cheng, \{Mu Jeng\} and Nielsen, \{Robert J.\} and Petasis, \{Nicos A.\} and Goddard, \{William A.\} and Periana, \{Roy A.\}",

year = "2011",

month = apr,

day = "1",

doi = "10.1016/j.molcata.2011.01.029",

language = "English",

volume = "339",

pages = "17--23",

journal = "Journal of Molecular Catalysis A: Chemical",

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number = "1-2",

}

Young, KJH, Lokare, KS, Leung, CH, Cheng, MJ, Nielsen, RJ, Petasis, NA, Goddard, WA & Periana, RA 2011, 'Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange', Journal of Molecular Catalysis A: Chemical, vol. 339, no. 1-2, pp. 17-23. https://doi.org/10.1016/j.molcata.2011.01.029

Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange. / Young, Kenneth J.H.; Lokare, Kapil S.; Leung, Chin Hin et al.
In: Journal of Molecular Catalysis A: Chemical, Vol. 339, No. 1-2, 01.04.2011, p. 17-23.

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

TY - JOUR

T1 - Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange

AU - Young, Kenneth J.H.

AU - Lokare, Kapil S.

AU - Leung, Chin Hin

AU - Cheng, Mu Jeng

AU - Nielsen, Robert J.

AU - Petasis, Nicos A.

AU - Goddard, William A.

AU - Periana, Roy A.

PY - 2011/4/1

Y1 - 2011/4/1

N2 - Using tridentate, neutral PyBox ligands, several new osmium and ruthenium complexes [M(PyBox)Cl2(C2H4), where M = Ru, Os] have been prepared, all thermally stable. Some of these PyBox compounds are active for C-H activation of benzene. The Os(PyBox)Cl2(C 2H4) complex was characterized by X-ray diffraction. DFT calculations (B3LYP and M06 including Poisson-Boltzmann solvation) corroborate that the Os/PyBox complex in acetic acid (ΔG‡ = 32.0 kcal/mol) is more reactive for benzene C-H activation than Ru/PyBox in basic conditions (ΔG‡ = 34.8 kcal/mol at pH = 13). The stability of hydroxide- and chloride-bridged dinuclear resting states determines calculated barriers.

AB - Using tridentate, neutral PyBox ligands, several new osmium and ruthenium complexes [M(PyBox)Cl2(C2H4), where M = Ru, Os] have been prepared, all thermally stable. Some of these PyBox compounds are active for C-H activation of benzene. The Os(PyBox)Cl2(C 2H4) complex was characterized by X-ray diffraction. DFT calculations (B3LYP and M06 including Poisson-Boltzmann solvation) corroborate that the Os/PyBox complex in acetic acid (ΔG‡ = 32.0 kcal/mol) is more reactive for benzene C-H activation than Ru/PyBox in basic conditions (ΔG‡ = 34.8 kcal/mol at pH = 13). The stability of hydroxide- and chloride-bridged dinuclear resting states determines calculated barriers.

KW - C-H activation

KW - Osmium

KW - PyBox

KW - Ruthenium

U2 - 10.1016/j.molcata.2011.01.029

DO - 10.1016/j.molcata.2011.01.029

M3 - Article

AN - SCOPUS:79954582106

SN - 1381-1169

VL - 339

SP - 17

EP - 23

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

IS - 1-2

ER -

Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange

Abstract

Keywords

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