Synthesis of Unsymmetrical Bis(phosphine) Oxides and Their Phosphines via Secondary Phosphine Oxide Precursors

James R. Pedroarena; Bryan P. Nell; Lev N. Zakharov; David R. Tyler

doi:10.1007/s10904-019-01288-9

Synthesis of Unsymmetrical Bis(phosphine) Oxides and Their Phosphines via Secondary Phosphine Oxide Precursors

James R. Pedroarena, Bryan P. Nell, Lev N. Zakharov, David R. Tyler

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

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Abstract

The unsymmetrical bidentate phosphine ligands (Me)₂PCH₂CH₂CH₂P(Et)₂ (14), (Me)₂PCH₂CH₂CH₂P(iPr)₂ (15), (Me)₂PCH₂CH₂CH₂P(Cy)₂ (16), and (Me)₂PCH₂CH₂CH₂P(Ph)₂ (17) were synthesized using air–stable phosphine oxide intermediates. In the first step, sodium phosphinites formed by deprotonation of (Me)₂P(O)H, (Et)₂P(O)H, and (iPr)₂P(O)H were alkylated by 1-bromo-3-chloropropane. The different substitution rates of the chloride and bromide groups allowed the isolation of the intermediates (Me)₂P(O)CH₂CH₂CH₂Cl (2), (Et)₂P(O)CH₂CH₂CH₂Cl (3), and (iPr)₂P(O)CH₂CH₂CH₂Cl (4). Subsequent reaction of (Me)₂P(O)CH₂CH₂CH₂Cl (2) with the sodium phosphinites generated from (Et)₂P(O)H, (iPr)₂P(O)H, (^tBu)₂P(O)H, (Cy)₂P(O)H, or (Ph)₂P(O)H gave unsymmetrical bidentate phosphine oxides; reduction of these oxides yielded the unsymmetrical phosphines. The unsymmetrical bidentate phosphines react with metal salts to form complexes. X-ray crystal structures of cis-Pt((Me)₂P(CH₂CH₂CH₂)P(iPr)₂)Cl₂ (20) and racemic [Cu^I((Me)₂P(CH₂CH₂CH₂)P(Ph)₂)]Cl (21) were obtained. The kinetics and scope of the synthetic route were also explored. Experiments showed that the rate of substitution of the alkyl chloride group in (R)₂P(O)CH₂CH₂CH₂Cl-type oxides increases relative to unsubstituted alkyl chlorides due to the presence of the phosphonyl group on one end of the molecule. The scope of the reaction involving 1,2-dihaloalkanes was also investigated, and it was found that the reaction mixture of sodium dimethylphosphinite and 1,2-dihaloalkanes formed tetramethylbis(phosphine) monoxide (22), which decomposes on work-up to give complex reaction mixtures.

Original language	English (US)
Pages (from-to)	196-205
Number of pages	10
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume	30
Issue number	1
DOIs	https://doi.org/10.1007/s10904-019-01288-9
State	Published - Jan 1 2020

Bibliographical note

Funding Information:
Acknowledgment is made to the NSF (CHE-1503550) for the support of this research. The project described was supported, in part, by the Oregon State University Research Office. The content is solely the responsibility of the authors and does not necessarily represent the official views of the OSU Mass Spectrometry Center. The authors acknowledge the OSU Mass Spectrometry Center at Oregon State University and specific institutional instrument grants. Orbitrap Fusion Lumos—NIH #1S10OD020111-01, Waters Ion Mobility ToF Mass Spectrometer—NIH #1S10RR025628-01, Applied Biosystems 4000Qtrap—NIH #1S10RR022589-01, ABSciex Triple ToF 5600—NIH #1S10RR027878-01. Dillon Bryant, Daniel Berg, and Alexi Overland are acknowledged for their contributions to this project.

Funding Information:
Acknowledgment is made to the NSF (CHE-1503550) for the support of this research. The project described was supported, in part, by the Oregon State University Research Office. The content is solely the responsibility of the authors and does not necessarily represent the official views of the OSU Mass Spectrometry Center. The authors acknowledge the OSU Mass Spectrometry Center at Oregon State University and specific institutional instrument grants. Orbitrap Fusion Lumos?NIH #1S10OD020111-01, Waters Ion Mobility ToF Mass Spectrometer?NIH #1S10RR025628-01, Applied Biosystems 4000Qtrap?NIH #1S10RR022589-01, ABSciex Triple ToF 5600?NIH #1S10RR027878-01. Dillon Bryant, Daniel Berg, and Alexi Overland are acknowledged for their contributions to this project.

Publisher Copyright:
© 2019, Springer Science+Business Media, LLC, part of Springer Nature.

Keywords

Heteroleptic phosphines
Phosphine ligands
Phosphinite anions
Unsymmetrical phosphine oxides
Unsymmetrical phosphines

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title = "Synthesis of Unsymmetrical Bis(phosphine) Oxides and Their Phosphines via Secondary Phosphine Oxide Precursors",

abstract = "The unsymmetrical bidentate phosphine ligands (Me)2PCH2CH2CH2P(Et)2 (14), (Me)2PCH2CH2CH2P(iPr)2 (15), (Me)2PCH2CH2CH2P(Cy)2 (16), and (Me)2PCH2CH2CH2P(Ph)2 (17) were synthesized using air–stable phosphine oxide intermediates. In the first step, sodium phosphinites formed by deprotonation of (Me)2P(O)H, (Et)2P(O)H, and (iPr)2P(O)H were alkylated by 1-bromo-3-chloropropane. The different substitution rates of the chloride and bromide groups allowed the isolation of the intermediates (Me)2P(O)CH2CH2CH2Cl (2), (Et)2P(O)CH2CH2CH2Cl (3), and (iPr)2P(O)CH2CH2CH2Cl (4). Subsequent reaction of (Me)2P(O)CH2CH2CH2Cl (2) with the sodium phosphinites generated from (Et)2P(O)H, (iPr)2P(O)H, (tBu)2P(O)H, (Cy)2P(O)H, or (Ph)2P(O)H gave unsymmetrical bidentate phosphine oxides; reduction of these oxides yielded the unsymmetrical phosphines. The unsymmetrical bidentate phosphines react with metal salts to form complexes. X-ray crystal structures of cis-Pt((Me)2P(CH2CH2CH2)P(iPr)2)Cl2 (20) and racemic [CuI((Me)2P(CH2CH2CH2)P(Ph)2)]Cl (21) were obtained. The kinetics and scope of the synthetic route were also explored. Experiments showed that the rate of substitution of the alkyl chloride group in (R)2P(O)CH2CH2CH2Cl-type oxides increases relative to unsubstituted alkyl chlorides due to the presence of the phosphonyl group on one end of the molecule. The scope of the reaction involving 1,2-dihaloalkanes was also investigated, and it was found that the reaction mixture of sodium dimethylphosphinite and 1,2-dihaloalkanes formed tetramethylbis(phosphine) monoxide (22), which decomposes on work-up to give complex reaction mixtures.",

keywords = "Heteroleptic phosphines, Phosphine ligands, Phosphinite anions, Unsymmetrical phosphine oxides, Unsymmetrical phosphines",

author = "Pedroarena, {James R.} and Nell, {Bryan P.} and Zakharov, {Lev N.} and Tyler, {David R.}",

note = "Funding Information: Acknowledgment is made to the NSF (CHE-1503550) for the support of this research. The project described was supported, in part, by the Oregon State University Research Office. The content is solely the responsibility of the authors and does not necessarily represent the official views of the OSU Mass Spectrometry Center. The authors acknowledge the OSU Mass Spectrometry Center at Oregon State University and specific institutional instrument grants. Orbitrap Fusion Lumos—NIH #1S10OD020111-01, Waters Ion Mobility ToF Mass Spectrometer—NIH #1S10RR025628-01, Applied Biosystems 4000Qtrap—NIH #1S10RR022589-01, ABSciex Triple ToF 5600—NIH #1S10RR027878-01. Dillon Bryant, Daniel Berg, and Alexi Overland are acknowledged for their contributions to this project. Funding Information: Acknowledgment is made to the NSF (CHE-1503550) for the support of this research. The project described was supported, in part, by the Oregon State University Research Office. The content is solely the responsibility of the authors and does not necessarily represent the official views of the OSU Mass Spectrometry Center. The authors acknowledge the OSU Mass Spectrometry Center at Oregon State University and specific institutional instrument grants. Orbitrap Fusion Lumos?NIH #1S10OD020111-01, Waters Ion Mobility ToF Mass Spectrometer?NIH #1S10RR025628-01, Applied Biosystems 4000Qtrap?NIH #1S10RR022589-01, ABSciex Triple ToF 5600?NIH #1S10RR027878-01. Dillon Bryant, Daniel Berg, and Alexi Overland are acknowledged for their contributions to this project. Publisher Copyright: {\textcopyright} 2019, Springer Science+Business Media, LLC, part of Springer Nature.",

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AU - Pedroarena, James R.

AU - Nell, Bryan P.

AU - Zakharov, Lev N.

AU - Tyler, David R.

N1 - Funding Information: Acknowledgment is made to the NSF (CHE-1503550) for the support of this research. The project described was supported, in part, by the Oregon State University Research Office. The content is solely the responsibility of the authors and does not necessarily represent the official views of the OSU Mass Spectrometry Center. The authors acknowledge the OSU Mass Spectrometry Center at Oregon State University and specific institutional instrument grants. Orbitrap Fusion Lumos—NIH #1S10OD020111-01, Waters Ion Mobility ToF Mass Spectrometer—NIH #1S10RR025628-01, Applied Biosystems 4000Qtrap—NIH #1S10RR022589-01, ABSciex Triple ToF 5600—NIH #1S10RR027878-01. Dillon Bryant, Daniel Berg, and Alexi Overland are acknowledged for their contributions to this project. Funding Information: Acknowledgment is made to the NSF (CHE-1503550) for the support of this research. The project described was supported, in part, by the Oregon State University Research Office. The content is solely the responsibility of the authors and does not necessarily represent the official views of the OSU Mass Spectrometry Center. The authors acknowledge the OSU Mass Spectrometry Center at Oregon State University and specific institutional instrument grants. Orbitrap Fusion Lumos?NIH #1S10OD020111-01, Waters Ion Mobility ToF Mass Spectrometer?NIH #1S10RR025628-01, Applied Biosystems 4000Qtrap?NIH #1S10RR022589-01, ABSciex Triple ToF 5600?NIH #1S10RR027878-01. Dillon Bryant, Daniel Berg, and Alexi Overland are acknowledged for their contributions to this project. Publisher Copyright: © 2019, Springer Science+Business Media, LLC, part of Springer Nature.

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N2 - The unsymmetrical bidentate phosphine ligands (Me)2PCH2CH2CH2P(Et)2 (14), (Me)2PCH2CH2CH2P(iPr)2 (15), (Me)2PCH2CH2CH2P(Cy)2 (16), and (Me)2PCH2CH2CH2P(Ph)2 (17) were synthesized using air–stable phosphine oxide intermediates. In the first step, sodium phosphinites formed by deprotonation of (Me)2P(O)H, (Et)2P(O)H, and (iPr)2P(O)H were alkylated by 1-bromo-3-chloropropane. The different substitution rates of the chloride and bromide groups allowed the isolation of the intermediates (Me)2P(O)CH2CH2CH2Cl (2), (Et)2P(O)CH2CH2CH2Cl (3), and (iPr)2P(O)CH2CH2CH2Cl (4). Subsequent reaction of (Me)2P(O)CH2CH2CH2Cl (2) with the sodium phosphinites generated from (Et)2P(O)H, (iPr)2P(O)H, (tBu)2P(O)H, (Cy)2P(O)H, or (Ph)2P(O)H gave unsymmetrical bidentate phosphine oxides; reduction of these oxides yielded the unsymmetrical phosphines. The unsymmetrical bidentate phosphines react with metal salts to form complexes. X-ray crystal structures of cis-Pt((Me)2P(CH2CH2CH2)P(iPr)2)Cl2 (20) and racemic [CuI((Me)2P(CH2CH2CH2)P(Ph)2)]Cl (21) were obtained. The kinetics and scope of the synthetic route were also explored. Experiments showed that the rate of substitution of the alkyl chloride group in (R)2P(O)CH2CH2CH2Cl-type oxides increases relative to unsubstituted alkyl chlorides due to the presence of the phosphonyl group on one end of the molecule. The scope of the reaction involving 1,2-dihaloalkanes was also investigated, and it was found that the reaction mixture of sodium dimethylphosphinite and 1,2-dihaloalkanes formed tetramethylbis(phosphine) monoxide (22), which decomposes on work-up to give complex reaction mixtures.

AB - The unsymmetrical bidentate phosphine ligands (Me)2PCH2CH2CH2P(Et)2 (14), (Me)2PCH2CH2CH2P(iPr)2 (15), (Me)2PCH2CH2CH2P(Cy)2 (16), and (Me)2PCH2CH2CH2P(Ph)2 (17) were synthesized using air–stable phosphine oxide intermediates. In the first step, sodium phosphinites formed by deprotonation of (Me)2P(O)H, (Et)2P(O)H, and (iPr)2P(O)H were alkylated by 1-bromo-3-chloropropane. The different substitution rates of the chloride and bromide groups allowed the isolation of the intermediates (Me)2P(O)CH2CH2CH2Cl (2), (Et)2P(O)CH2CH2CH2Cl (3), and (iPr)2P(O)CH2CH2CH2Cl (4). Subsequent reaction of (Me)2P(O)CH2CH2CH2Cl (2) with the sodium phosphinites generated from (Et)2P(O)H, (iPr)2P(O)H, (tBu)2P(O)H, (Cy)2P(O)H, or (Ph)2P(O)H gave unsymmetrical bidentate phosphine oxides; reduction of these oxides yielded the unsymmetrical phosphines. The unsymmetrical bidentate phosphines react with metal salts to form complexes. X-ray crystal structures of cis-Pt((Me)2P(CH2CH2CH2)P(iPr)2)Cl2 (20) and racemic [CuI((Me)2P(CH2CH2CH2)P(Ph)2)]Cl (21) were obtained. The kinetics and scope of the synthetic route were also explored. Experiments showed that the rate of substitution of the alkyl chloride group in (R)2P(O)CH2CH2CH2Cl-type oxides increases relative to unsubstituted alkyl chlorides due to the presence of the phosphonyl group on one end of the molecule. The scope of the reaction involving 1,2-dihaloalkanes was also investigated, and it was found that the reaction mixture of sodium dimethylphosphinite and 1,2-dihaloalkanes formed tetramethylbis(phosphine) monoxide (22), which decomposes on work-up to give complex reaction mixtures.

KW - Heteroleptic phosphines

KW - Phosphine ligands

KW - Phosphinite anions

KW - Unsymmetrical phosphine oxides

KW - Unsymmetrical phosphines

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Synthesis of Unsymmetrical Bis(phosphine) Oxides and Their Phosphines via Secondary Phosphine Oxide Precursors

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