Dibenzo[b,f]phosphepines: Novel phosphane-olefin ligands for transition metals

Volodymyr Lyaskovskyy; Relinde J.A. Van Dijk-Moes; Sebastian Burck; Wojciech I. Dzik; Martin Lutz; Andreas W. Ehlers; J. Chris Slootweg; Bas De Bruin; Koop Lammertsma

doi:10.1021/om301012z

Dibenzo[b,f]phosphepines: Novel phosphane-olefin ligands for transition metals

Volodymyr Lyaskovskyy, Relinde J.A. Van Dijk-Moes, Sebastian Burck, Wojciech I. Dzik, Martin Lutz, Andreas W. Ehlers, J. Chris Slootweg, Bas De Bruin, Koop Lammertsma

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

28 Citations (Scopus)

Abstract

New, stable heterobidentate phosphane-olefin ligands based on the dibenzo[b,f]phosphepine backbone are reported together with their redox properties and coordination chemistry to rhodium(I). The X-ray crystal structures and DFT calculations show different conformations for the P-phenyl (6a) and P-mesityl (6b) derivatives. Cyclic voltammetry (vs Fc/Fc⁺) of 6a supported by UV-vis spectroelectrochemistry showed two cathodic waves, a reversible one at E_1/2 = -2.62 V (I_f/I_b = 1.0) and a quasi-reversible (I_f/I_b ≈ 1.2) one at E _1/2 = -3.03 V. Reduction with sodium afforded a mixture of the radical anion [6a^•]^-, characterized by EPR spectroscopy, and dianion [6a]^2-, for which an X-ray crystal structure was obtained. Both 6a and 6b bind to Rh^I centers, giving rise to 3:1 (8a) and 2:1 (8b) ligand:Rh complexes, respectively. Two dibenzo[b,f]phosphepines in 8a and 8b act as heterobidentate ligands in which both the phosphorus atom and the olefinic double bond coordinate to rhodium, but the third ligand in 8a binds as a monodentate P-donor. The cyclic voltammogram of 8b showed two close-lying waves, a one-electron reversible wave at -1.45 V and a two-electron quasi-reversible wave at -1.80 V (I_f/I_b ≈ 1.3). 8a showed a reversible wave at -1.71 V and irreversible waves at lower potentials.

Original language	English
Pages (from-to)	363-373
Number of pages	11
Journal	Organometallics
Volume	32
Issue number	2
DOIs	https://doi.org/10.1021/om301012z
Publication status	Published - 28 Jan 2013
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om301012z

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@article{a86346ccb31a40689bd0522e7b712455,

title = "Dibenzo[b,f]phosphepines: Novel phosphane-olefin ligands for transition metals",

abstract = "New, stable heterobidentate phosphane-olefin ligands based on the dibenzo[b,f]phosphepine backbone are reported together with their redox properties and coordination chemistry to rhodium(I). The X-ray crystal structures and DFT calculations show different conformations for the P-phenyl (6a) and P-mesityl (6b) derivatives. Cyclic voltammetry (vs Fc/Fc+) of 6a supported by UV-vis spectroelectrochemistry showed two cathodic waves, a reversible one at E1/2 = -2.62 V (If/Ib = 1.0) and a quasi-reversible (If/Ib ≈ 1.2) one at E 1/2 = -3.03 V. Reduction with sodium afforded a mixture of the radical anion [6a•]-, characterized by EPR spectroscopy, and dianion [6a]2-, for which an X-ray crystal structure was obtained. Both 6a and 6b bind to RhI centers, giving rise to 3:1 (8a) and 2:1 (8b) ligand:Rh complexes, respectively. Two dibenzo[b,f]phosphepines in 8a and 8b act as heterobidentate ligands in which both the phosphorus atom and the olefinic double bond coordinate to rhodium, but the third ligand in 8a binds as a monodentate P-donor. The cyclic voltammogram of 8b showed two close-lying waves, a one-electron reversible wave at -1.45 V and a two-electron quasi-reversible wave at -1.80 V (If/Ib ≈ 1.3). 8a showed a reversible wave at -1.71 V and irreversible waves at lower potentials.",

author = "Volodymyr Lyaskovskyy and {Van Dijk-Moes}, {Relinde J.A.} and Sebastian Burck and Dzik, {Wojciech I.} and Martin Lutz and Ehlers, {Andreas W.} and Slootweg, {J. Chris} and {De Bruin}, Bas and Koop Lammertsma",

year = "2013",

month = jan,

day = "28",

doi = "10.1021/om301012z",

language = "English",

volume = "32",

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journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - Dibenzo[b,f]phosphepines

T2 - Novel phosphane-olefin ligands for transition metals

AU - Lyaskovskyy, Volodymyr

AU - Van Dijk-Moes, Relinde J.A.

AU - Burck, Sebastian

AU - Dzik, Wojciech I.

AU - Lutz, Martin

AU - Ehlers, Andreas W.

AU - Slootweg, J. Chris

AU - De Bruin, Bas

AU - Lammertsma, Koop

PY - 2013/1/28

Y1 - 2013/1/28

N2 - New, stable heterobidentate phosphane-olefin ligands based on the dibenzo[b,f]phosphepine backbone are reported together with their redox properties and coordination chemistry to rhodium(I). The X-ray crystal structures and DFT calculations show different conformations for the P-phenyl (6a) and P-mesityl (6b) derivatives. Cyclic voltammetry (vs Fc/Fc+) of 6a supported by UV-vis spectroelectrochemistry showed two cathodic waves, a reversible one at E1/2 = -2.62 V (If/Ib = 1.0) and a quasi-reversible (If/Ib ≈ 1.2) one at E 1/2 = -3.03 V. Reduction with sodium afforded a mixture of the radical anion [6a•]-, characterized by EPR spectroscopy, and dianion [6a]2-, for which an X-ray crystal structure was obtained. Both 6a and 6b bind to RhI centers, giving rise to 3:1 (8a) and 2:1 (8b) ligand:Rh complexes, respectively. Two dibenzo[b,f]phosphepines in 8a and 8b act as heterobidentate ligands in which both the phosphorus atom and the olefinic double bond coordinate to rhodium, but the third ligand in 8a binds as a monodentate P-donor. The cyclic voltammogram of 8b showed two close-lying waves, a one-electron reversible wave at -1.45 V and a two-electron quasi-reversible wave at -1.80 V (If/Ib ≈ 1.3). 8a showed a reversible wave at -1.71 V and irreversible waves at lower potentials.

AB - New, stable heterobidentate phosphane-olefin ligands based on the dibenzo[b,f]phosphepine backbone are reported together with their redox properties and coordination chemistry to rhodium(I). The X-ray crystal structures and DFT calculations show different conformations for the P-phenyl (6a) and P-mesityl (6b) derivatives. Cyclic voltammetry (vs Fc/Fc+) of 6a supported by UV-vis spectroelectrochemistry showed two cathodic waves, a reversible one at E1/2 = -2.62 V (If/Ib = 1.0) and a quasi-reversible (If/Ib ≈ 1.2) one at E 1/2 = -3.03 V. Reduction with sodium afforded a mixture of the radical anion [6a•]-, characterized by EPR spectroscopy, and dianion [6a]2-, for which an X-ray crystal structure was obtained. Both 6a and 6b bind to RhI centers, giving rise to 3:1 (8a) and 2:1 (8b) ligand:Rh complexes, respectively. Two dibenzo[b,f]phosphepines in 8a and 8b act as heterobidentate ligands in which both the phosphorus atom and the olefinic double bond coordinate to rhodium, but the third ligand in 8a binds as a monodentate P-donor. The cyclic voltammogram of 8b showed two close-lying waves, a one-electron reversible wave at -1.45 V and a two-electron quasi-reversible wave at -1.80 V (If/Ib ≈ 1.3). 8a showed a reversible wave at -1.71 V and irreversible waves at lower potentials.

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U2 - 10.1021/om301012z

DO - 10.1021/om301012z

M3 - Article

AN - SCOPUS:84872981245

SN - 0276-7333

VL - 32

SP - 363

EP - 373

JO - Organometallics

JF - Organometallics

IS - 2

ER -

Dibenzo[b,f]phosphepines: Novel phosphane-olefin ligands for transition metals

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