Synthesis, characterization, and electrochemistry of a series of iron (ii) complexes containing self-assembled 1,5-diaza-3,7-diphosphabicyclo[3.3.1]nonane ligands

Andrew D. Burrows; Ross W. Harrington; Andrew S. Kirk; Mary F. Mahon; Frank Marken; John E. Warren; Michael K. Whittlesey

doi:10.1021/ic900874f

Synthesis, characterization, and electrochemistry of a series of iron (ii) complexes containing self-assembled 1,5-diaza-3,7-diphosphabicyclo[3.3.1]nonane ligands

Andrew D. Burrows, Ross W. Harrington, Andrew S. Kirk, Mary F. Mahon, Frank Marken, John E. Warren, Michael K. Whittlesey

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

Abstract

The reaction between PPh(CH2OH)2, iron(II) sulfate, ammonium sulfate, and formaldehyde in aqueous solution gives the iron(II) complex [Fe(κ2-O2SO2)L2] (1), where L is the bidentate phosphine ligand 3,7-diphenyl-1,5-diaza-3, 7-diphosphabicyclo[3.3.1]nonane. During the course of the reaction, the ligand L self-assembles on the metal center. The reaction between PPh(CH 2OH)2, iron(II) chloride, ammonium chloride, and formaldehyde under similar conditions gives cis-[FeCl2L2] (cis-2). The complex cis-2 is converted into trans-2 In Et2O, whereas in water it is converted into cis-[Fe(OH2)2L 2]2+, though both of these interconversions are reversible. The chloro ligands in cis-2 are readily displaced by reaction with thiocyanate, azide, and carbonate to give cis- and trans-[Fe(NCS) 2L2] (cis- and trans-3), cis- and trans-[Fe(N 3)2L2] (cis- and trans-4), and [Fe(κ2-O2CO)L2] (5), respectively. The complex cis-2 reacts with CO in water to give trans-[FeCl(CO)L2]Cl (trans-6), whereas trans-2 reacts with CO in diethyl ether to give cis-[FeCl(CO)L2]Cl (cis-6), though cis-6 isomerizes in water to form trans-6. The reaction of cis-2 with sodium borohydride gives the hydride chloride complex trans-[FeCl(H)L2] (7). Electrochemical studies have been undertaken on complexes 1, cis-2, and 7. These reveal reversible oxidations for cis-2 and 7, with the latter giving rise to an unusual 17-electron iron(III) hydride chloride complex. Crystal structures have been obtained for 1, trans-2, trans-2,5, and 7. © 2009 American Chemical Society.

Original language	English
Pages (from-to)	9924-9935
Number of pages	11
Journal	Inorganic Chemistry: including bioinorganic chemistry
Volume	48
Issue number	20
DOIs	https://doi.org/10.1021/ic900874f
Publication status	Published - 2009

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CCDC 767364: Experimental Crystal Structure Determination
Burrows, A. D. (Contributor), Harrington, R. W. (Contributor), Kirk, A. S. (Contributor), Mahon, M. F. (Contributor), Marken, F. (Contributor), Warren, J. (Contributor) & Whittlesey, M. K. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2010
DOI: 10.5517/cctrhpq, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cctrhpq&sid=DataCite
Dataset
CCDC 767362: Experimental Crystal Structure Determination
Burrows, A. D. (Contributor), Harrington, R. W. (Contributor), Kirk, A. S. (Contributor), Mahon, M. F. (Contributor), Marken, F. (Contributor), Warren, J. (Contributor) & Whittlesey, M. K. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2010
DOI: 10.5517/cctrhmn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cctrhmn&sid=DataCite
Dataset
CCDC 767365: Experimental Crystal Structure Determination
Burrows, A. D. (Contributor), Harrington, R. W. (Contributor), Kirk, A. S. (Contributor), Mahon, M. F. (Contributor), Marken, F. (Contributor), Warren, J. (Contributor) & Whittlesey, M. K. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2010
DOI: 10.5517/cctrhqr, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cctrhqr&sid=DataCite
Dataset

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Burrows, A. D., Harrington, R. W., Kirk, A. S., Mahon, M. F., Marken, F., Warren, J. E., & Whittlesey, M. K. (2009). Synthesis, characterization, and electrochemistry of a series of iron (ii) complexes containing self-assembled 1,5-diaza-3,7-diphosphabicyclo[3.3.1]nonane ligands. Inorganic Chemistry: including bioinorganic chemistry , 48(20), 9924-9935. https://doi.org/10.1021/ic900874f

@article{bb5e925f93204e278a928742b8221acb,

title = "Synthesis, characterization, and electrochemistry of a series of iron (ii) complexes containing self-assembled 1,5-diaza-3,7-diphosphabicyclo[3.3.1]nonane ligands",

abstract = "The reaction between PPh(CH2OH)2, iron(II) sulfate, ammonium sulfate, and formaldehyde in aqueous solution gives the iron(II) complex [Fe(κ2-O2SO2)L2] (1), where L is the bidentate phosphine ligand 3,7-diphenyl-1,5-diaza-3, 7-diphosphabicyclo[3.3.1]nonane. During the course of the reaction, the ligand L self-assembles on the metal center. The reaction between PPh(CH 2OH)2, iron(II) chloride, ammonium chloride, and formaldehyde under similar conditions gives cis-[FeCl2L2] (cis-2). The complex cis-2 is converted into trans-2 In Et2O, whereas in water it is converted into cis-[Fe(OH2)2L 2]2+, though both of these interconversions are reversible. The chloro ligands in cis-2 are readily displaced by reaction with thiocyanate, azide, and carbonate to give cis- and trans-[Fe(NCS) 2L2] (cis- and trans-3), cis- and trans-[Fe(N 3)2L2] (cis- and trans-4), and [Fe(κ2-O2CO)L2] (5), respectively. The complex cis-2 reacts with CO in water to give trans-[FeCl(CO)L2]Cl (trans-6), whereas trans-2 reacts with CO in diethyl ether to give cis-[FeCl(CO)L2]Cl (cis-6), though cis-6 isomerizes in water to form trans-6. The reaction of cis-2 with sodium borohydride gives the hydride chloride complex trans-[FeCl(H)L2] (7). Electrochemical studies have been undertaken on complexes 1, cis-2, and 7. These reveal reversible oxidations for cis-2 and 7, with the latter giving rise to an unusual 17-electron iron(III) hydride chloride complex. Crystal structures have been obtained for 1, trans-2, trans-2,5, and 7. {\textcopyright} 2009 American Chemical Society.",

author = "Burrows, {Andrew D.} and Harrington, {Ross W.} and Kirk, {Andrew S.} and Mahon, {Mary F.} and Frank Marken and Warren, {John E.} and Whittlesey, {Michael K.}",

note = "20",

year = "2009",

doi = "10.1021/ic900874f",

language = "English",

volume = "48",

pages = "9924--9935",

journal = "Inorganic Chemistry: including bioinorganic chemistry ",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

}

Burrows, AD, Harrington, RW, Kirk, AS, Mahon, MF, Marken, F, Warren, JE & Whittlesey, MK 2009, 'Synthesis, characterization, and electrochemistry of a series of iron (ii) complexes containing self-assembled 1,5-diaza-3,7-diphosphabicyclo[3.3.1]nonane ligands', Inorganic Chemistry: including bioinorganic chemistry , vol. 48, no. 20, pp. 9924-9935. https://doi.org/10.1021/ic900874f

Synthesis, characterization, and electrochemistry of a series of iron (ii) complexes containing self-assembled 1,5-diaza-3,7-diphosphabicyclo[3.3.1]nonane ligands. / Burrows, Andrew D.; Harrington, Ross W.; Kirk, Andrew S. et al.
In: Inorganic Chemistry: including bioinorganic chemistry , Vol. 48, No. 20, 2009, p. 9924-9935.

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

TY - JOUR

T1 - Synthesis, characterization, and electrochemistry of a series of iron (ii) complexes containing self-assembled 1,5-diaza-3,7-diphosphabicyclo[3.3.1]nonane ligands

AU - Burrows, Andrew D.

AU - Harrington, Ross W.

AU - Kirk, Andrew S.

AU - Mahon, Mary F.

AU - Marken, Frank

AU - Warren, John E.

AU - Whittlesey, Michael K.

N1 - 20

PY - 2009

Y1 - 2009

N2 - The reaction between PPh(CH2OH)2, iron(II) sulfate, ammonium sulfate, and formaldehyde in aqueous solution gives the iron(II) complex [Fe(κ2-O2SO2)L2] (1), where L is the bidentate phosphine ligand 3,7-diphenyl-1,5-diaza-3, 7-diphosphabicyclo[3.3.1]nonane. During the course of the reaction, the ligand L self-assembles on the metal center. The reaction between PPh(CH 2OH)2, iron(II) chloride, ammonium chloride, and formaldehyde under similar conditions gives cis-[FeCl2L2] (cis-2). The complex cis-2 is converted into trans-2 In Et2O, whereas in water it is converted into cis-[Fe(OH2)2L 2]2+, though both of these interconversions are reversible. The chloro ligands in cis-2 are readily displaced by reaction with thiocyanate, azide, and carbonate to give cis- and trans-[Fe(NCS) 2L2] (cis- and trans-3), cis- and trans-[Fe(N 3)2L2] (cis- and trans-4), and [Fe(κ2-O2CO)L2] (5), respectively. The complex cis-2 reacts with CO in water to give trans-[FeCl(CO)L2]Cl (trans-6), whereas trans-2 reacts with CO in diethyl ether to give cis-[FeCl(CO)L2]Cl (cis-6), though cis-6 isomerizes in water to form trans-6. The reaction of cis-2 with sodium borohydride gives the hydride chloride complex trans-[FeCl(H)L2] (7). Electrochemical studies have been undertaken on complexes 1, cis-2, and 7. These reveal reversible oxidations for cis-2 and 7, with the latter giving rise to an unusual 17-electron iron(III) hydride chloride complex. Crystal structures have been obtained for 1, trans-2, trans-2,5, and 7. © 2009 American Chemical Society.

AB - The reaction between PPh(CH2OH)2, iron(II) sulfate, ammonium sulfate, and formaldehyde in aqueous solution gives the iron(II) complex [Fe(κ2-O2SO2)L2] (1), where L is the bidentate phosphine ligand 3,7-diphenyl-1,5-diaza-3, 7-diphosphabicyclo[3.3.1]nonane. During the course of the reaction, the ligand L self-assembles on the metal center. The reaction between PPh(CH 2OH)2, iron(II) chloride, ammonium chloride, and formaldehyde under similar conditions gives cis-[FeCl2L2] (cis-2). The complex cis-2 is converted into trans-2 In Et2O, whereas in water it is converted into cis-[Fe(OH2)2L 2]2+, though both of these interconversions are reversible. The chloro ligands in cis-2 are readily displaced by reaction with thiocyanate, azide, and carbonate to give cis- and trans-[Fe(NCS) 2L2] (cis- and trans-3), cis- and trans-[Fe(N 3)2L2] (cis- and trans-4), and [Fe(κ2-O2CO)L2] (5), respectively. The complex cis-2 reacts with CO in water to give trans-[FeCl(CO)L2]Cl (trans-6), whereas trans-2 reacts with CO in diethyl ether to give cis-[FeCl(CO)L2]Cl (cis-6), though cis-6 isomerizes in water to form trans-6. The reaction of cis-2 with sodium borohydride gives the hydride chloride complex trans-[FeCl(H)L2] (7). Electrochemical studies have been undertaken on complexes 1, cis-2, and 7. These reveal reversible oxidations for cis-2 and 7, with the latter giving rise to an unusual 17-electron iron(III) hydride chloride complex. Crystal structures have been obtained for 1, trans-2, trans-2,5, and 7. © 2009 American Chemical Society.

U2 - 10.1021/ic900874f

DO - 10.1021/ic900874f

M3 - Article

SN - 0020-1669

VL - 48

SP - 9924

EP - 9935

JO - Inorganic Chemistry: including bioinorganic chemistry

JF - Inorganic Chemistry: including bioinorganic chemistry

IS - 20

ER -

Synthesis, characterization, and electrochemistry of a series of iron (ii) complexes containing self-assembled 1,5-diaza-3,7-diphosphabicyclo[3.3.1]nonane ligands

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CCDC 767364: Experimental Crystal Structure Determination

CCDC 767362: Experimental Crystal Structure Determination

CCDC 767365: Experimental Crystal Structure Determination

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