Synthesis, structures, photophysical properties, and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes

M. Mustafa Cetin; Sara Shafiei-Haghighi; Jiazhen Chen; Sheng Zhang; Amanda C. Miller; Daniel K. Unruh; Dominick J. Casadonte; Tracy Lynn Lohr; Tobin J. Marks; Michael F. Mayer; J. Fraser Stoddart; Michael Findlater

doi:10.1002/pol.20190276

Synthesis, structures, photophysical properties, and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes

M. Mustafa Cetin, Sara Shafiei-Haghighi, Jiazhen Chen, Sheng Zhang, Amanda C. Miller, Daniel K. Unruh, Dominick J. Casadonte, Tracy Lynn Lohr, Tobin J. Marks, Michael F. Mayer, J. Fraser Stoddart^*, Michael Findlater

^*Corresponding author for this work

Chemistry

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

7 Scopus citations

Abstract

The syntheses of the 2,9-dimesityl-1,10-phenanthroline (dmesp) metal complexes, [Cu(dmesp)(MeCN)]PF₆ (1), [Cu(dmesp)₂]PF₆ (2), Fe(dmesp)Cl₂ (3), Co(dmesp)Cl₂ (4), Ni(dmesp)Cl₂ (5), Zn(dmesp)Cl₂ (6), Pd(dmesp)MeCl (7), Cu(dmesp)Cl (8), and Pd(dmesp)₂Cl₂ (9), in good to high yields are described. These complexes were characterized by ¹H and ¹³C NMR spectroscopy, HR–MS (ESI and/or APPI), and elemental analysis (CHN). The solid-state structures of complexes 1–8 were determined by single-crystal X-ray analysis and their photophysical properties were also characterized. To demonstrate the versatility of this new platform, complexes 3–5, 8, and 9 were employed in the catalytic oligomerization of ethylene using modified methyl aluminoxane (MMAO) as the cocatalyst, where Co(II) and Ni(II) complexes (4 and 5, respectively) were found to exhibit moderate selectivity for catalytic dimerization of ethylene to butenes over tri- or tetramerization. Complex 8 is an effective catalyst of both the commonly encountered “click” reaction and amine arylation chemistries. Complexes 6 and 9 were found to be excellent catalysts for Friedel-Crafts alkylation and Suzuki-Miyaura coupling, respectively.

Original language	English (US)
Pages (from-to)	1130-1143
Number of pages	14
Journal	Journal of Polymer Science
Volume	58
Issue number	8
DOIs	https://doi.org/10.1002/pol.20190276
State	Published - Apr 15 2020

Funding

Financial support from the National Science Foundation (MFM research grant CHE‐0847736, MF research grant CHE‐1554906, and NMR grant CHE‐1048553), the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS), and Northwestern University (NU) are gratefully acknowledged. We also thank the Department of Chemistry and Biochemistry of Texas Tech University and the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University (NU) for use of the instrumental facilities. Financial support from the National Science Foundation (MFM research grant CHE-0847736, MF research grant CHE-1554906, and NMR grant CHE-1048553), the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS), and Northwestern University (NU) are gratefully acknowledged. We also thank the Department of Chemistry and Biochemistry of Texas Tech University and the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University (NU) for use of the instrumental facilities. Northwestern University (NU); Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS); National Science Foundation, Grant/Award Numbers: CHE‐1048553, 1554906, CHE‐0847736 Funding information

Keywords

catalysis
oligomerization
phenanthroline
transition metals

ASJC Scopus subject areas

Materials Chemistry
Polymers and Plastics
Physical and Theoretical Chemistry

Access to Document

10.1002/pol.20190276

Cite this

Cetin, M. M., Shafiei-Haghighi, S., Chen, J., Zhang, S., Miller, A. C., Unruh, D. K., Casadonte, D. J., Lohr, T. L., Marks, T. J., Mayer, M. F., Stoddart, J. F., & Findlater, M. (2020). Synthesis, structures, photophysical properties, and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes. Journal of Polymer Science, 58(8), 1130-1143. https://doi.org/10.1002/pol.20190276

@article{ac07e781cc3d4bdb9d4ffa3c97c9ccc6,

title = "Synthesis, structures, photophysical properties, and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes",

abstract = "The syntheses of the 2,9-dimesityl-1,10-phenanthroline (dmesp) metal complexes, [Cu(dmesp)(MeCN)]PF6 (1), [Cu(dmesp)2]PF6 (2), Fe(dmesp)Cl2 (3), Co(dmesp)Cl2 (4), Ni(dmesp)Cl2 (5), Zn(dmesp)Cl2 (6), Pd(dmesp)MeCl (7), Cu(dmesp)Cl (8), and Pd(dmesp)2Cl2 (9), in good to high yields are described. These complexes were characterized by 1H and 13C NMR spectroscopy, HR–MS (ESI and/or APPI), and elemental analysis (CHN). The solid-state structures of complexes 1–8 were determined by single-crystal X-ray analysis and their photophysical properties were also characterized. To demonstrate the versatility of this new platform, complexes 3–5, 8, and 9 were employed in the catalytic oligomerization of ethylene using modified methyl aluminoxane (MMAO) as the cocatalyst, where Co(II) and Ni(II) complexes (4 and 5, respectively) were found to exhibit moderate selectivity for catalytic dimerization of ethylene to butenes over tri- or tetramerization. Complex 8 is an effective catalyst of both the commonly encountered “click” reaction and amine arylation chemistries. Complexes 6 and 9 were found to be excellent catalysts for Friedel-Crafts alkylation and Suzuki-Miyaura coupling, respectively.",

keywords = "catalysis, oligomerization, phenanthroline, transition metals",

author = "Cetin, {M. Mustafa} and Sara Shafiei-Haghighi and Jiazhen Chen and Sheng Zhang and Miller, {Amanda C.} and Unruh, {Daniel K.} and Casadonte, {Dominick J.} and Lohr, {Tracy Lynn} and Marks, {Tobin J.} and Mayer, {Michael F.} and Stoddart, {J. Fraser} and Michael Findlater",

note = "Funding Information: Financial support from the National Science Foundation (MFM research grant CHE‐0847736, MF research grant CHE‐1554906, and NMR grant CHE‐1048553), the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS), and Northwestern University (NU) are gratefully acknowledged. We also thank the Department of Chemistry and Biochemistry of Texas Tech University and the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University (NU) for use of the instrumental facilities. Funding Information: Financial support from the National Science Foundation (MFM research grant CHE-0847736, MF research grant CHE-1554906, and NMR grant CHE-1048553), the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS), and Northwestern University (NU) are gratefully acknowledged. We also thank the Department of Chemistry and Biochemistry of Texas Tech University and the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University (NU) for use of the instrumental facilities. Funding Information: Northwestern University (NU); Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS); National Science Foundation, Grant/Award Numbers: CHE‐1048553, 1554906, CHE‐0847736 Funding information Publisher Copyright: {\textcopyright} 2020 Wiley Periodicals, Inc.",

year = "2020",

month = apr,

day = "15",

doi = "10.1002/pol.20190276",

language = "English (US)",

volume = "58",

pages = "1130--1143",

journal = "Journal of Polymer Science",

issn = "2642-4150",

publisher = "John Wiley & Sons Inc.",

number = "8",

}

Cetin, MM, Shafiei-Haghighi, S, Chen, J, Zhang, S, Miller, AC, Unruh, DK, Casadonte, DJ, Lohr, TL, Marks, TJ, Mayer, MF, Stoddart, JF & Findlater, M 2020, 'Synthesis, structures, photophysical properties, and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes', Journal of Polymer Science, vol. 58, no. 8, pp. 1130-1143. https://doi.org/10.1002/pol.20190276

TY - JOUR

T1 - Synthesis, structures, photophysical properties, and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes

AU - Cetin, M. Mustafa

AU - Shafiei-Haghighi, Sara

AU - Chen, Jiazhen

AU - Zhang, Sheng

AU - Miller, Amanda C.

AU - Unruh, Daniel K.

AU - Casadonte, Dominick J.

AU - Lohr, Tracy Lynn

AU - Marks, Tobin J.

AU - Mayer, Michael F.

AU - Stoddart, J. Fraser

AU - Findlater, Michael

N1 - Funding Information: Financial support from the National Science Foundation (MFM research grant CHE‐0847736, MF research grant CHE‐1554906, and NMR grant CHE‐1048553), the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS), and Northwestern University (NU) are gratefully acknowledged. We also thank the Department of Chemistry and Biochemistry of Texas Tech University and the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University (NU) for use of the instrumental facilities. Funding Information: Financial support from the National Science Foundation (MFM research grant CHE-0847736, MF research grant CHE-1554906, and NMR grant CHE-1048553), the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS), and Northwestern University (NU) are gratefully acknowledged. We also thank the Department of Chemistry and Biochemistry of Texas Tech University and the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University (NU) for use of the instrumental facilities. Funding Information: Northwestern University (NU); Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACTS); National Science Foundation, Grant/Award Numbers: CHE‐1048553, 1554906, CHE‐0847736 Funding information Publisher Copyright: © 2020 Wiley Periodicals, Inc.

PY - 2020/4/15

Y1 - 2020/4/15

N2 - The syntheses of the 2,9-dimesityl-1,10-phenanthroline (dmesp) metal complexes, [Cu(dmesp)(MeCN)]PF6 (1), [Cu(dmesp)2]PF6 (2), Fe(dmesp)Cl2 (3), Co(dmesp)Cl2 (4), Ni(dmesp)Cl2 (5), Zn(dmesp)Cl2 (6), Pd(dmesp)MeCl (7), Cu(dmesp)Cl (8), and Pd(dmesp)2Cl2 (9), in good to high yields are described. These complexes were characterized by 1H and 13C NMR spectroscopy, HR–MS (ESI and/or APPI), and elemental analysis (CHN). The solid-state structures of complexes 1–8 were determined by single-crystal X-ray analysis and their photophysical properties were also characterized. To demonstrate the versatility of this new platform, complexes 3–5, 8, and 9 were employed in the catalytic oligomerization of ethylene using modified methyl aluminoxane (MMAO) as the cocatalyst, where Co(II) and Ni(II) complexes (4 and 5, respectively) were found to exhibit moderate selectivity for catalytic dimerization of ethylene to butenes over tri- or tetramerization. Complex 8 is an effective catalyst of both the commonly encountered “click” reaction and amine arylation chemistries. Complexes 6 and 9 were found to be excellent catalysts for Friedel-Crafts alkylation and Suzuki-Miyaura coupling, respectively.

AB - The syntheses of the 2,9-dimesityl-1,10-phenanthroline (dmesp) metal complexes, [Cu(dmesp)(MeCN)]PF6 (1), [Cu(dmesp)2]PF6 (2), Fe(dmesp)Cl2 (3), Co(dmesp)Cl2 (4), Ni(dmesp)Cl2 (5), Zn(dmesp)Cl2 (6), Pd(dmesp)MeCl (7), Cu(dmesp)Cl (8), and Pd(dmesp)2Cl2 (9), in good to high yields are described. These complexes were characterized by 1H and 13C NMR spectroscopy, HR–MS (ESI and/or APPI), and elemental analysis (CHN). The solid-state structures of complexes 1–8 were determined by single-crystal X-ray analysis and their photophysical properties were also characterized. To demonstrate the versatility of this new platform, complexes 3–5, 8, and 9 were employed in the catalytic oligomerization of ethylene using modified methyl aluminoxane (MMAO) as the cocatalyst, where Co(II) and Ni(II) complexes (4 and 5, respectively) were found to exhibit moderate selectivity for catalytic dimerization of ethylene to butenes over tri- or tetramerization. Complex 8 is an effective catalyst of both the commonly encountered “click” reaction and amine arylation chemistries. Complexes 6 and 9 were found to be excellent catalysts for Friedel-Crafts alkylation and Suzuki-Miyaura coupling, respectively.

KW - catalysis

KW - oligomerization

KW - phenanthroline

KW - transition metals

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U2 - 10.1002/pol.20190276

DO - 10.1002/pol.20190276

M3 - Article

AN - SCOPUS:85092428626

SN - 2642-4150

VL - 58

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EP - 1143

JO - Journal of Polymer Science

JF - Journal of Polymer Science

IS - 8

ER -

Synthesis, structures, photophysical properties, and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes

Abstract

Funding

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ASJC Scopus subject areas

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CCDC 1571435: Experimental Crystal Structure Determination

CCDC 1571440: Experimental Crystal Structure Determination

CCDC 1571439: Experimental Crystal Structure Determination

Cite this

Synthesis, structures, photophysical properties, and catalytic characteristics of 2,9-dimesityl-1,10-phenanthroline (dmesp) transition metal complexes

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1571435: Experimental Crystal Structure Determination

CCDC 1571440: Experimental Crystal Structure Determination

CCDC 1571439: Experimental Crystal Structure Determination

Cite this