Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S2PPh2)3 and V(Se2PPh2)3: A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E2PPh2)3 (E=S, Se)

Christine A. Phipps; Joanna M. Rosenberger; McKenzie M. Miller; Sean R. Parkin; Jessie L. Brown

doi:10.1002/zaac.202000396

Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S₂PPh₂)₃ and V(Se₂PPh₂)₃: A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E₂PPh₂)₃ (E=S, Se)

Christine A. Phipps, Joanna M. Rosenberger, McKenzie M. Miller, Sean R. Parkin, Jessie L. Brown

Chemistry

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

Abstract

Addition of the potassium dichalcogenidodiphenylphosphinate salts, KE₂PPh₂ (E=S, Se), to either the THF solvate of vanadium(III) chloride or unsolvated chromium(III) chloride results in rapid ligand substitution and the formation of a series of closely-related trivalent, neutral mononuclear complexes, M(E₂PPh₂)₃ (M=V, Cr; E=S, Se), isolated in modest to good yield. The metal dichalcogenidophosphinate complexes reported herein were characterized by IR, UV-vis, and ¹H NMR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the comparative analysis includes the structural and spectroscopic studies of two rare V(III) dithio- and diseleno-phosphinate VE₆ cores, as well as, two previously known CrE₆ analogues. In the solid-state the title complexes exhibit trigonal distortion from octahedral with torsion angles ranging from 43(2) to 50.3(6)° and structural parameters consistent with ligation of progressively ‘softer’ chalcogen-donors.

Original language	English
Pages (from-to)	1182-1192
Number of pages	11
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	647
Issue number	11
DOIs	https://doi.org/10.1002/zaac.202000396
State	Published - Jun 11 2021

Bibliographical note

Funding Information:
All synthetic work was performed at Transylvania University and financially supported by the David and Betty Jones Faculty Development Fund. X‐ray crystallography was performed at the X‐Ray Facility at the University of Kentucky and financially supported by the NSF MRI program, award CHE‐1625732. We thank A. J. Gaunt for their insightful comments and J. E. McDonald (in memoriam) for their encouragement of this work.

Publisher Copyright:
© 2020 Wiley-VCH GmbH

Keywords

chromium(III)
diphenyldiselenophosphinate complexes
diphenyldithiophosphinate complexes
vanadium(III)

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/zaac.202000396

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Phipps, C. A., Rosenberger, J. M., Miller, M. M., Parkin, S. R., & Brown, J. L. (2021). Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S₂PPh₂)₃ and V(Se₂PPh₂)₃: A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E₂PPh₂)₃ (E=S, Se). Zeitschrift fur Anorganische und Allgemeine Chemie, 647(11), 1182-1192. https://doi.org/10.1002/zaac.202000396

Phipps, Christine A. ; Rosenberger, Joanna M. ; Miller, McKenzie M. et al. / Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S₂PPh₂)₃ and V(Se₂PPh₂)₃ : A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E₂PPh₂)₃ (E=S, Se). In: Zeitschrift fur Anorganische und Allgemeine Chemie. 2021 ; Vol. 647, No. 11. pp. 1182-1192.

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title = "Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S2PPh2)3 and V(Se2PPh2)3: A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E2PPh2)3 (E=S, Se)",

abstract = "Addition of the potassium dichalcogenidodiphenylphosphinate salts, KE2PPh2 (E=S, Se), to either the THF solvate of vanadium(III) chloride or unsolvated chromium(III) chloride results in rapid ligand substitution and the formation of a series of closely-related trivalent, neutral mononuclear complexes, M(E2PPh2)3 (M=V, Cr; E=S, Se), isolated in modest to good yield. The metal dichalcogenidophosphinate complexes reported herein were characterized by IR, UV-vis, and 1H NMR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the comparative analysis includes the structural and spectroscopic studies of two rare V(III) dithio- and diseleno-phosphinate VE6 cores, as well as, two previously known CrE6 analogues. In the solid-state the title complexes exhibit trigonal distortion from octahedral with torsion angles ranging from 43(2) to 50.3(6)° and structural parameters consistent with ligation of progressively {\textquoteleft}softer{\textquoteright} chalcogen-donors.",

keywords = "chromium(III), diphenyldiselenophosphinate complexes, diphenyldithiophosphinate complexes, vanadium(III)",

author = "Phipps, {Christine A.} and Rosenberger, {Joanna M.} and Miller, {McKenzie M.} and Parkin, {Sean R.} and Brown, {Jessie L.}",

note = "Funding Information: All synthetic work was performed at Transylvania University and financially supported by the David and Betty Jones Faculty Development Fund. X‐ray crystallography was performed at the X‐Ray Facility at the University of Kentucky and financially supported by the NSF MRI program, award CHE‐1625732. We thank A. J. Gaunt for their insightful comments and J. E. McDonald (in memoriam) for their encouragement of this work. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

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Phipps, CA, Rosenberger, JM, Miller, MM, Parkin, SR & Brown, JL 2021, 'Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S₂PPh₂)₃ and V(Se₂PPh₂)₃: A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E₂PPh₂)₃ (E=S, Se)', Zeitschrift fur Anorganische und Allgemeine Chemie, vol. 647, no. 11, pp. 1182-1192. https://doi.org/10.1002/zaac.202000396

Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S₂PPh₂)₃ and V(Se₂PPh₂)₃ : A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E₂PPh₂)₃ (E=S, Se). / Phipps, Christine A.; Rosenberger, Joanna M.; Miller, McKenzie M. et al.

In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 647, No. 11, 11.06.2021, p. 1182-1192.

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

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T2 - A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E2PPh2)3 (E=S, Se)

AU - Phipps, Christine A.

AU - Rosenberger, Joanna M.

AU - Miller, McKenzie M.

AU - Parkin, Sean R.

AU - Brown, Jessie L.

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PY - 2021/6/11

Y1 - 2021/6/11

N2 - Addition of the potassium dichalcogenidodiphenylphosphinate salts, KE2PPh2 (E=S, Se), to either the THF solvate of vanadium(III) chloride or unsolvated chromium(III) chloride results in rapid ligand substitution and the formation of a series of closely-related trivalent, neutral mononuclear complexes, M(E2PPh2)3 (M=V, Cr; E=S, Se), isolated in modest to good yield. The metal dichalcogenidophosphinate complexes reported herein were characterized by IR, UV-vis, and 1H NMR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the comparative analysis includes the structural and spectroscopic studies of two rare V(III) dithio- and diseleno-phosphinate VE6 cores, as well as, two previously known CrE6 analogues. In the solid-state the title complexes exhibit trigonal distortion from octahedral with torsion angles ranging from 43(2) to 50.3(6)° and structural parameters consistent with ligation of progressively ‘softer’ chalcogen-donors.

AB - Addition of the potassium dichalcogenidodiphenylphosphinate salts, KE2PPh2 (E=S, Se), to either the THF solvate of vanadium(III) chloride or unsolvated chromium(III) chloride results in rapid ligand substitution and the formation of a series of closely-related trivalent, neutral mononuclear complexes, M(E2PPh2)3 (M=V, Cr; E=S, Se), isolated in modest to good yield. The metal dichalcogenidophosphinate complexes reported herein were characterized by IR, UV-vis, and 1H NMR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the comparative analysis includes the structural and spectroscopic studies of two rare V(III) dithio- and diseleno-phosphinate VE6 cores, as well as, two previously known CrE6 analogues. In the solid-state the title complexes exhibit trigonal distortion from octahedral with torsion angles ranging from 43(2) to 50.3(6)° and structural parameters consistent with ligation of progressively ‘softer’ chalcogen-donors.

KW - chromium(III)

KW - diphenyldiselenophosphinate complexes

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Phipps CA, Rosenberger JM, Miller MM, Parkin SR, Brown JL. Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S₂PPh₂)₃ and V(Se₂PPh₂)₃: A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E₂PPh₂)₃ (E=S, Se). Zeitschrift fur Anorganische und Allgemeine Chemie. 2021 Jun 11;647(11):1182-1192. doi: 10.1002/zaac.202000396