Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: Synthesis, structure and spectroscopic investigation

Tapash Chakraborty; Kriti Srivastava; Harkesh B. Singh; Ray J. Butcher

doi:10.1016/j.jorganchem.2011.04.018

Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: Synthesis, structure and spectroscopic investigation

Tapash Chakraborty, Kriti Srivastava, Harkesh B. Singh, Ray J. Butcher

Chemistry (Twin Cities)

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

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Abstract

Oxidative addition of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide to Pd(PPh₃)₄ provided two different mononuclear palladium selenolato complexes, Pd(Se∩N)(PPh₃)Cl (4) [Se∩N = chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolate] and Pd(Se∩N)(Se∩N*) (PPh₃) (5) [Se∩N = chelating, Se∩N* = non-chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolato ligand] in dicholoromethane and toluene respectively. Complex 4 has also been synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl)phenylselenenyl chloride to Pd(PPh ₃)₄. The bromo and iodo analogs of 4 (9 and 10) were similarly synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl) phenylselenenyl bromide and iodide, respectively to Pd(PPh₃) ₄. The oxidative addition of 2-(N,N-dimethylaminomethyl) phenylselenenyl bromide and iodide to Pd(PPh₃)₄ afforded mononuclear palladium selenolate complexes, Pd(Se∩N)(PPh₃)X (13 and 14) [Se∩N = chelating 2-(N,N-dimethylaminomethyl)phenylselenolate, X = Br: 13, X = I: 14]. The reactions of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide and bis[2-(N,N-dimethylaminomethyl)phenyl] diselenide with Pd(COD)Cl₂ provided dinuclear selenolato-bridged complexes [PdCl(Se∩N)]₂ (15) [Se∩N = chelating 2-(4,4-dimethyl-2- oxazolinyl)phenylselenolate] and [PdCl(Se∩N)]₂ (19) [Se∩N = chelating 2-(N,N-dimethylaminomethyl)phenylselenolate] respectively. The complexes were characterized by elemental analysis and NMR (¹H and ⁷⁷Se) spectroscopy. Complexes 4 and 5 were also characterized by mass spectrometry. Molecular structures of 4, 5, 9, 14 and 15 have been established by single crystal X-ray diffraction analysis. Complexes 4 and 9 are isomorphous and crystallize in the space group P2₁/c of the monoclinic system where the selenolato and halo ligands are trans to each other. Complex 5 crystallizes in the space group P2₁/n of the monoclinic system where one chelating and one non-chelating selenolato ligands are trans to each other. Mononuclear complex 14 and binuclear centrosymmetric complex 15 crystallize in the P1 space group of the triclinic system.

Original language	English (US)
Pages (from-to)	2782-2788
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	696
Issue number	15-16
DOIs	https://doi.org/10.1016/j.jorganchem.2011.04.018
State	Published - Aug 1 2011

Bibliographical note

Funding Information:
We are thankful to the Department of Science and Technology (DST), India for funding this work. Additional help from the Sophisticated Analytical Instrument Facility (SAIF), Indian Institute of Technology, Bombay, for 300 MHz NMR spectroscopy is gratefully acknowledged. T. C. and K. S. are also grateful to the Council of Scientific and Industrial Research, India for providing fellowship.

Keywords

Diselenide
Oxidative addition
Palladium
Selenenyl halide
Selenolate

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10.1016/j.jorganchem.2011.04.018

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Chakraborty, T., Srivastava, K., Singh, H. B., & Butcher, R. J. (2011). Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: Synthesis, structure and spectroscopic investigation. Journal of Organometallic Chemistry, 696(15-16), 2782-2788. https://doi.org/10.1016/j.jorganchem.2011.04.018

Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: Synthesis, structure and spectroscopic investigation. / Chakraborty, Tapash; Srivastava, Kriti; Singh, Harkesh B. et al.
In: Journal of Organometallic Chemistry, Vol. 696, No. 15-16, 01.08.2011, p. 2782-2788.

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

Chakraborty, T, Srivastava, K, Singh, HB & Butcher, RJ 2011, 'Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: Synthesis, structure and spectroscopic investigation', Journal of Organometallic Chemistry, vol. 696, no. 15-16, pp. 2782-2788. https://doi.org/10.1016/j.jorganchem.2011.04.018

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title = "Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: Synthesis, structure and spectroscopic investigation",

abstract = "Oxidative addition of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide to Pd(PPh3)4 provided two different mononuclear palladium selenolato complexes, Pd(Se∩N)(PPh3)Cl (4) [Se∩N = chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolate] and Pd(Se∩N)(Se∩N*) (PPh3) (5) [Se∩N = chelating, Se∩N* = non-chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolato ligand] in dicholoromethane and toluene respectively. Complex 4 has also been synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl)phenylselenenyl chloride to Pd(PPh 3)4. The bromo and iodo analogs of 4 (9 and 10) were similarly synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl) phenylselenenyl bromide and iodide, respectively to Pd(PPh3) 4. The oxidative addition of 2-(N,N-dimethylaminomethyl) phenylselenenyl bromide and iodide to Pd(PPh3)4 afforded mononuclear palladium selenolate complexes, Pd(Se∩N)(PPh3)X (13 and 14) [Se∩N = chelating 2-(N,N-dimethylaminomethyl)phenylselenolate, X = Br: 13, X = I: 14]. The reactions of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide and bis[2-(N,N-dimethylaminomethyl)phenyl] diselenide with Pd(COD)Cl2 provided dinuclear selenolato-bridged complexes [PdCl(Se∩N)]2 (15) [Se∩N = chelating 2-(4,4-dimethyl-2- oxazolinyl)phenylselenolate] and [PdCl(Se∩N)]2 (19) [Se∩N = chelating 2-(N,N-dimethylaminomethyl)phenylselenolate] respectively. The complexes were characterized by elemental analysis and NMR (1H and 77Se) spectroscopy. Complexes 4 and 5 were also characterized by mass spectrometry. Molecular structures of 4, 5, 9, 14 and 15 have been established by single crystal X-ray diffraction analysis. Complexes 4 and 9 are isomorphous and crystallize in the space group P21/c of the monoclinic system where the selenolato and halo ligands are trans to each other. Complex 5 crystallizes in the space group P21/n of the monoclinic system where one chelating and one non-chelating selenolato ligands are trans to each other. Mononuclear complex 14 and binuclear centrosymmetric complex 15 crystallize in the P1 space group of the triclinic system.",

keywords = "Diselenide, Oxidative addition, Palladium, Selenenyl halide, Selenolate",

author = "Tapash Chakraborty and Kriti Srivastava and Singh, {Harkesh B.} and Butcher, {Ray J.}",

note = "Funding Information: We are thankful to the Department of Science and Technology (DST), India for funding this work. Additional help from the Sophisticated Analytical Instrument Facility (SAIF), Indian Institute of Technology, Bombay, for 300 MHz NMR spectroscopy is gratefully acknowledged. T. C. and K. S. are also grateful to the Council of Scientific and Industrial Research, India for providing fellowship. ",

year = "2011",

month = aug,

day = "1",

doi = "10.1016/j.jorganchem.2011.04.018",

language = "English (US)",

volume = "696",

pages = "2782--2788",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "15-16",

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TY - JOUR

T1 - Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides

T2 - Synthesis, structure and spectroscopic investigation

AU - Chakraborty, Tapash

AU - Srivastava, Kriti

AU - Singh, Harkesh B.

AU - Butcher, Ray J.

N1 - Funding Information: We are thankful to the Department of Science and Technology (DST), India for funding this work. Additional help from the Sophisticated Analytical Instrument Facility (SAIF), Indian Institute of Technology, Bombay, for 300 MHz NMR spectroscopy is gratefully acknowledged. T. C. and K. S. are also grateful to the Council of Scientific and Industrial Research, India for providing fellowship.

PY - 2011/8/1

Y1 - 2011/8/1

N2 - Oxidative addition of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide to Pd(PPh3)4 provided two different mononuclear palladium selenolato complexes, Pd(Se∩N)(PPh3)Cl (4) [Se∩N = chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolate] and Pd(Se∩N)(Se∩N*) (PPh3) (5) [Se∩N = chelating, Se∩N* = non-chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolato ligand] in dicholoromethane and toluene respectively. Complex 4 has also been synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl)phenylselenenyl chloride to Pd(PPh 3)4. The bromo and iodo analogs of 4 (9 and 10) were similarly synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl) phenylselenenyl bromide and iodide, respectively to Pd(PPh3) 4. The oxidative addition of 2-(N,N-dimethylaminomethyl) phenylselenenyl bromide and iodide to Pd(PPh3)4 afforded mononuclear palladium selenolate complexes, Pd(Se∩N)(PPh3)X (13 and 14) [Se∩N = chelating 2-(N,N-dimethylaminomethyl)phenylselenolate, X = Br: 13, X = I: 14]. The reactions of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide and bis[2-(N,N-dimethylaminomethyl)phenyl] diselenide with Pd(COD)Cl2 provided dinuclear selenolato-bridged complexes [PdCl(Se∩N)]2 (15) [Se∩N = chelating 2-(4,4-dimethyl-2- oxazolinyl)phenylselenolate] and [PdCl(Se∩N)]2 (19) [Se∩N = chelating 2-(N,N-dimethylaminomethyl)phenylselenolate] respectively. The complexes were characterized by elemental analysis and NMR (1H and 77Se) spectroscopy. Complexes 4 and 5 were also characterized by mass spectrometry. Molecular structures of 4, 5, 9, 14 and 15 have been established by single crystal X-ray diffraction analysis. Complexes 4 and 9 are isomorphous and crystallize in the space group P21/c of the monoclinic system where the selenolato and halo ligands are trans to each other. Complex 5 crystallizes in the space group P21/n of the monoclinic system where one chelating and one non-chelating selenolato ligands are trans to each other. Mononuclear complex 14 and binuclear centrosymmetric complex 15 crystallize in the P1 space group of the triclinic system.

AB - Oxidative addition of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide to Pd(PPh3)4 provided two different mononuclear palladium selenolato complexes, Pd(Se∩N)(PPh3)Cl (4) [Se∩N = chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolate] and Pd(Se∩N)(Se∩N*) (PPh3) (5) [Se∩N = chelating, Se∩N* = non-chelating 2-(4,4-dimethyl-2-oxazolinyl)phenylselenolato ligand] in dicholoromethane and toluene respectively. Complex 4 has also been synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl)phenylselenenyl chloride to Pd(PPh 3)4. The bromo and iodo analogs of 4 (9 and 10) were similarly synthesized by the oxidative addition of 2-(4,4-dimethyl-2-oxazolinyl) phenylselenenyl bromide and iodide, respectively to Pd(PPh3) 4. The oxidative addition of 2-(N,N-dimethylaminomethyl) phenylselenenyl bromide and iodide to Pd(PPh3)4 afforded mononuclear palladium selenolate complexes, Pd(Se∩N)(PPh3)X (13 and 14) [Se∩N = chelating 2-(N,N-dimethylaminomethyl)phenylselenolate, X = Br: 13, X = I: 14]. The reactions of bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide and bis[2-(N,N-dimethylaminomethyl)phenyl] diselenide with Pd(COD)Cl2 provided dinuclear selenolato-bridged complexes [PdCl(Se∩N)]2 (15) [Se∩N = chelating 2-(4,4-dimethyl-2- oxazolinyl)phenylselenolate] and [PdCl(Se∩N)]2 (19) [Se∩N = chelating 2-(N,N-dimethylaminomethyl)phenylselenolate] respectively. The complexes were characterized by elemental analysis and NMR (1H and 77Se) spectroscopy. Complexes 4 and 5 were also characterized by mass spectrometry. Molecular structures of 4, 5, 9, 14 and 15 have been established by single crystal X-ray diffraction analysis. Complexes 4 and 9 are isomorphous and crystallize in the space group P21/c of the monoclinic system where the selenolato and halo ligands are trans to each other. Complex 5 crystallizes in the space group P21/n of the monoclinic system where one chelating and one non-chelating selenolato ligands are trans to each other. Mononuclear complex 14 and binuclear centrosymmetric complex 15 crystallize in the P1 space group of the triclinic system.

KW - Diselenide

KW - Oxidative addition

KW - Palladium

KW - Selenenyl halide

KW - Selenolate

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VL - 696

SP - 2782

EP - 2788

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 15-16

ER -

Palladium selenolates via oxidative addition of organylselenenyl halides to palladium(0) precursor and via cleavage reaction of diselenides: Synthesis, structure and spectroscopic investigation

Abstract

Bibliographical note

Keywords

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