Synthesis, structure, spectroscopy, and reactivity of oxapentadienyl- cobalt-phosphine complexes

John R. Bleeke; Bryn L. Lutes; Michael Lipschutz; Donastas Sakellariou-Thompson; John Seonghyun Lee; Nigam P. Rath

doi:10.1021/om100361a

Synthesis, structure, spectroscopy, and reactivity of oxapentadienyl- cobalt-phosphine complexes

John R. Bleeke
, Bryn L. Lutes
, Michael Lipschutz
, Donastas Sakellariou-Thompson
, John Seonghyun Lee
, Nigam P. Rath

Department of Chemistry

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

14 Scopus citations

Abstract

The first examples of oxapentadienyl-cobalt complexes have been synthesized and structurally characterized. Treatment of (Cl)Co(PMe₃) ₃ with potassium oxapentadienide produces ((1,2,3-η)-5- oxapentadienyl)Co(PMe₃)₃ (1), while the reaction of (Cl)Co(PMe₃)₃ with potassium 2,4-dimethyloxapentadienide generates ((1,2,3-η)-2,4-dimethyl-5-oxapentadienyl)Co(PMe₃) ₃ (2). Both 1 and 2 undergo ligand substitution reactions when treated with excess carbon monoxide. Compound 1 reacts with 1 equiv of CO to produce ((1,2,3-η)-5-oxapentadienyl)Co(PMe₃)₂(CO) (3), while 2 undergoes a double CO substitution to generate ((1,2,3-η)-2,4- dimethyl-5-oxapentadienyl)Co(PMe₃)(CO)₂ (4). Compound 3 can also be synthesized by reacting (Cl)Co(PMe₃)₂(CO) ₂ with potassium oxapentadienide, but the analogous reaction involving potassium 2,4-dimethyloxapentadienide results in reduction of the cobalt starting material and production of the Co(0) dimer (CO)(PMe ₃)₂Co(μ-CO)₂Co(PMe₃) ₂(CO) (5). Treatment of 1 with triflic acid (HO₃SCF ₃) or methyl triflate (MeO₃SCF₃) results in electrophilic attack at oxygen and production of (η⁴-butadienol) Co(PMe₃)₃⁺O₃SCF₃ ^- (6) or (η⁴-butadienyl methyl ether)Co(PMe ₃)₃⁺O₃SCF₃^- (7). Treatment of 2 with triflic acid or methyl triflate also results in electrophilic attack at oxygen; however, these products are unstable and rapidly lose their protonated or methylated ligands. The resulting Co(PMe ₃)₄⁺O₃SCF₃^-, generated in situ, reacts with excess carbon monoxide to produce Co(PMe ₃)₃(CO)₂⁺O₃SCF ₃^- (8). Compounds 1-8 have been characterized by single-crystal X-ray diffraction.

Original language	English
Pages (from-to)	5057-5067
Number of pages	11
Journal	Organometallics
Volume	29
Issue number	21
DOIs	https://doi.org/10.1021/om100361a
State	Published - Nov 8 2010

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@article{3d754d7612f74f3685b451c383331e23,

title = "Synthesis, structure, spectroscopy, and reactivity of oxapentadienyl- cobalt-phosphine complexes",

abstract = "The first examples of oxapentadienyl-cobalt complexes have been synthesized and structurally characterized. Treatment of (Cl)Co(PMe3) 3 with potassium oxapentadienide produces ((1,2,3-η)-5- oxapentadienyl)Co(PMe3)3 (1), while the reaction of (Cl)Co(PMe3)3 with potassium 2,4-dimethyloxapentadienide generates ((1,2,3-η)-2,4-dimethyl-5-oxapentadienyl)Co(PMe3) 3 (2). Both 1 and 2 undergo ligand substitution reactions when treated with excess carbon monoxide. Compound 1 reacts with 1 equiv of CO to produce ((1,2,3-η)-5-oxapentadienyl)Co(PMe3)2(CO) (3), while 2 undergoes a double CO substitution to generate ((1,2,3-η)-2,4- dimethyl-5-oxapentadienyl)Co(PMe3)(CO)2 (4). Compound 3 can also be synthesized by reacting (Cl)Co(PMe3)2(CO) 2 with potassium oxapentadienide, but the analogous reaction involving potassium 2,4-dimethyloxapentadienide results in reduction of the cobalt starting material and production of the Co(0) dimer (CO)(PMe 3)2Co(μ-CO)2Co(PMe3) 2(CO) (5). Treatment of 1 with triflic acid (HO3SCF 3) or methyl triflate (MeO3SCF3) results in electrophilic attack at oxygen and production of (η4-butadienol) Co(PMe3)3+O3SCF3 - (6) or (η4-butadienyl methyl ether)Co(PMe 3)3+O3SCF3- (7). Treatment of 2 with triflic acid or methyl triflate also results in electrophilic attack at oxygen; however, these products are unstable and rapidly lose their protonated or methylated ligands. The resulting Co(PMe 3)4+O3SCF3-, generated in situ, reacts with excess carbon monoxide to produce Co(PMe 3)3(CO)2+O3SCF 3- (8). Compounds 1-8 have been characterized by single-crystal X-ray diffraction.",

author = "Bleeke, \{John R.\} and Lutes, \{Bryn L.\} and Michael Lipschutz and Donastas Sakellariou-Thompson and Lee, \{John Seonghyun\} and Rath, \{Nigam P.\}",

year = "2010",

month = nov,

day = "8",

doi = "10.1021/om100361a",

language = "English",

volume = "29",

pages = "5057--5067",

journal = "Organometallics",

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TY - JOUR

T1 - Synthesis, structure, spectroscopy, and reactivity of oxapentadienyl- cobalt-phosphine complexes

AU - Bleeke, John R.

AU - Lutes, Bryn L.

AU - Lipschutz, Michael

AU - Sakellariou-Thompson, Donastas

AU - Lee, John Seonghyun

AU - Rath, Nigam P.

PY - 2010/11/8

Y1 - 2010/11/8

N2 - The first examples of oxapentadienyl-cobalt complexes have been synthesized and structurally characterized. Treatment of (Cl)Co(PMe3) 3 with potassium oxapentadienide produces ((1,2,3-η)-5- oxapentadienyl)Co(PMe3)3 (1), while the reaction of (Cl)Co(PMe3)3 with potassium 2,4-dimethyloxapentadienide generates ((1,2,3-η)-2,4-dimethyl-5-oxapentadienyl)Co(PMe3) 3 (2). Both 1 and 2 undergo ligand substitution reactions when treated with excess carbon monoxide. Compound 1 reacts with 1 equiv of CO to produce ((1,2,3-η)-5-oxapentadienyl)Co(PMe3)2(CO) (3), while 2 undergoes a double CO substitution to generate ((1,2,3-η)-2,4- dimethyl-5-oxapentadienyl)Co(PMe3)(CO)2 (4). Compound 3 can also be synthesized by reacting (Cl)Co(PMe3)2(CO) 2 with potassium oxapentadienide, but the analogous reaction involving potassium 2,4-dimethyloxapentadienide results in reduction of the cobalt starting material and production of the Co(0) dimer (CO)(PMe 3)2Co(μ-CO)2Co(PMe3) 2(CO) (5). Treatment of 1 with triflic acid (HO3SCF 3) or methyl triflate (MeO3SCF3) results in electrophilic attack at oxygen and production of (η4-butadienol) Co(PMe3)3+O3SCF3 - (6) or (η4-butadienyl methyl ether)Co(PMe 3)3+O3SCF3- (7). Treatment of 2 with triflic acid or methyl triflate also results in electrophilic attack at oxygen; however, these products are unstable and rapidly lose their protonated or methylated ligands. The resulting Co(PMe 3)4+O3SCF3-, generated in situ, reacts with excess carbon monoxide to produce Co(PMe 3)3(CO)2+O3SCF 3- (8). Compounds 1-8 have been characterized by single-crystal X-ray diffraction.

AB - The first examples of oxapentadienyl-cobalt complexes have been synthesized and structurally characterized. Treatment of (Cl)Co(PMe3) 3 with potassium oxapentadienide produces ((1,2,3-η)-5- oxapentadienyl)Co(PMe3)3 (1), while the reaction of (Cl)Co(PMe3)3 with potassium 2,4-dimethyloxapentadienide generates ((1,2,3-η)-2,4-dimethyl-5-oxapentadienyl)Co(PMe3) 3 (2). Both 1 and 2 undergo ligand substitution reactions when treated with excess carbon monoxide. Compound 1 reacts with 1 equiv of CO to produce ((1,2,3-η)-5-oxapentadienyl)Co(PMe3)2(CO) (3), while 2 undergoes a double CO substitution to generate ((1,2,3-η)-2,4- dimethyl-5-oxapentadienyl)Co(PMe3)(CO)2 (4). Compound 3 can also be synthesized by reacting (Cl)Co(PMe3)2(CO) 2 with potassium oxapentadienide, but the analogous reaction involving potassium 2,4-dimethyloxapentadienide results in reduction of the cobalt starting material and production of the Co(0) dimer (CO)(PMe 3)2Co(μ-CO)2Co(PMe3) 2(CO) (5). Treatment of 1 with triflic acid (HO3SCF 3) or methyl triflate (MeO3SCF3) results in electrophilic attack at oxygen and production of (η4-butadienol) Co(PMe3)3+O3SCF3 - (6) or (η4-butadienyl methyl ether)Co(PMe 3)3+O3SCF3- (7). Treatment of 2 with triflic acid or methyl triflate also results in electrophilic attack at oxygen; however, these products are unstable and rapidly lose their protonated or methylated ligands. The resulting Co(PMe 3)4+O3SCF3-, generated in situ, reacts with excess carbon monoxide to produce Co(PMe 3)3(CO)2+O3SCF 3- (8). Compounds 1-8 have been characterized by single-crystal X-ray diffraction.

UR - https://www.scopus.com/pages/publications/78149312721

U2 - 10.1021/om100361a

DO - 10.1021/om100361a

M3 - Article

AN - SCOPUS:78149312721

SN - 0276-7333

VL - 29

SP - 5057

EP - 5067

JO - Organometallics

JF - Organometallics

IS - 21

ER -

Synthesis, structure, spectroscopy, and reactivity of oxapentadienyl- cobalt-phosphine complexes

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