Stereochemical control of iron(II) complexes containing a diphosphine ligand with a pendant nitrogen base

Renee M. Henry, Richard K. Shoemaker, Rachel H. Newell, George M. Jacobsen, Daniel L DuBois, M. Rakowski DuBois

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

A series of cis and trans Fe(II) complexes containing the diphosphine ligand PNP (where PNP is bis((diethylphosphino)methyl)methylamine) have been prepared and isolated. These include cis-[Fe(PNP) 2(CH 3CN) 2](BF 4) 2 (3), cis-[Fe(PNP) 2(CH 3CN)(CO)](BF 4) 2 (4), trans-[Fe-(PNP)(dmpm)(CH 3CN) 2](BF 4) 2 (5), trans-Fe(PNP)(dmpm)Cl 2 (6), trans-[Fe(PNP)(dmpm) (CO)-Cl] 2[FeCl 4] (7), trans-HFe(PNP)(dmpm)Cl (8), and trans-[HFe(PNP)(dmpm)(CH 3CN)]BPh 4 (9) (where dmpm is bis(dimethylphosphino)methane). In addition, the cations trans-[HFe-(PNP)(dmpm) (CO)] + (10) and trans-[(H 2)Fe(PNP)(dmpm)(H)] + (11) have been observed in solution. These complexes all possess a pendant base that bridges the two phosphorus atoms of the PNP ligand. A cis geometry is observed for those complexes containing two PNP ligands, whereas a trans geometry is observed for the complexes containing one PNP ligand and one dmpm ligand. The molecular structures of cis-[Fe(PNP) 2(CH 3CN)(CO)](BPh 4) 2 and trans-[HFe(PNP)(dmpm) (CH 3CN)]BPh 4 have been confirmed by X-ray diffraction studies. Protonation of 5, 7, and 10 occurs at the nitrogen atom of the PNP ligand, and pK a values are reported for the corresponding protonated complexes. The formation of the dihydrogen complex [trans-[(H 2)Fe(PNP)(dmpm)(H)] + and the protonated PNHP complex trans-[HFe-(PNHP)(dmpm)(CO)] 2+ demonstrate that intramolecular heterolytic cleavage of the dihydrogen ligand can be controlled by varying the nature of the ligand trans to the incipient dihydrogen ligand.

Original languageEnglish
Pages (from-to)2481-2491
Number of pages11
JournalOrganometallics
Volume24
Issue number10
DOIs
Publication statusPublished - May 9 2005

Fingerprint

Nitrogen
Iron
Ligands
iron
nitrogen
ligands
Carbon Monoxide
methylidyne
Atoms
Geometry
Protonation
Methane
geometry
nitrogen atoms
Phosphorus
Molecular structure
phosphorus
Cations
cleavage
molecular structure

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Stereochemical control of iron(II) complexes containing a diphosphine ligand with a pendant nitrogen base. / Henry, Renee M.; Shoemaker, Richard K.; Newell, Rachel H.; Jacobsen, George M.; DuBois, Daniel L; DuBois, M. Rakowski.

In: Organometallics, Vol. 24, No. 10, 09.05.2005, p. 2481-2491.

Research output: Contribution to journalArticle

Henry, Renee M. ; Shoemaker, Richard K. ; Newell, Rachel H. ; Jacobsen, George M. ; DuBois, Daniel L ; DuBois, M. Rakowski. / Stereochemical control of iron(II) complexes containing a diphosphine ligand with a pendant nitrogen base. In: Organometallics. 2005 ; Vol. 24, No. 10. pp. 2481-2491.
@article{1406e00e78f24655a11161f0735dabdc,
title = "Stereochemical control of iron(II) complexes containing a diphosphine ligand with a pendant nitrogen base",
abstract = "A series of cis and trans Fe(II) complexes containing the diphosphine ligand PNP (where PNP is bis((diethylphosphino)methyl)methylamine) have been prepared and isolated. These include cis-[Fe(PNP) 2(CH 3CN) 2](BF 4) 2 (3), cis-[Fe(PNP) 2(CH 3CN)(CO)](BF 4) 2 (4), trans-[Fe-(PNP)(dmpm)(CH 3CN) 2](BF 4) 2 (5), trans-Fe(PNP)(dmpm)Cl 2 (6), trans-[Fe(PNP)(dmpm) (CO)-Cl] 2[FeCl 4] (7), trans-HFe(PNP)(dmpm)Cl (8), and trans-[HFe(PNP)(dmpm)(CH 3CN)]BPh 4 (9) (where dmpm is bis(dimethylphosphino)methane). In addition, the cations trans-[HFe-(PNP)(dmpm) (CO)] + (10) and trans-[(H 2)Fe(PNP)(dmpm)(H)] + (11) have been observed in solution. These complexes all possess a pendant base that bridges the two phosphorus atoms of the PNP ligand. A cis geometry is observed for those complexes containing two PNP ligands, whereas a trans geometry is observed for the complexes containing one PNP ligand and one dmpm ligand. The molecular structures of cis-[Fe(PNP) 2(CH 3CN)(CO)](BPh 4) 2 and trans-[HFe(PNP)(dmpm) (CH 3CN)]BPh 4 have been confirmed by X-ray diffraction studies. Protonation of 5, 7, and 10 occurs at the nitrogen atom of the PNP ligand, and pK a values are reported for the corresponding protonated complexes. The formation of the dihydrogen complex [trans-[(H 2)Fe(PNP)(dmpm)(H)] + and the protonated PNHP complex trans-[HFe-(PNHP)(dmpm)(CO)] 2+ demonstrate that intramolecular heterolytic cleavage of the dihydrogen ligand can be controlled by varying the nature of the ligand trans to the incipient dihydrogen ligand.",
author = "Henry, {Renee M.} and Shoemaker, {Richard K.} and Newell, {Rachel H.} and Jacobsen, {George M.} and DuBois, {Daniel L} and DuBois, {M. Rakowski}",
year = "2005",
month = "5",
day = "9",
doi = "10.1021/om050071c",
language = "English",
volume = "24",
pages = "2481--2491",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Stereochemical control of iron(II) complexes containing a diphosphine ligand with a pendant nitrogen base

AU - Henry, Renee M.

AU - Shoemaker, Richard K.

AU - Newell, Rachel H.

AU - Jacobsen, George M.

AU - DuBois, Daniel L

AU - DuBois, M. Rakowski

PY - 2005/5/9

Y1 - 2005/5/9

N2 - A series of cis and trans Fe(II) complexes containing the diphosphine ligand PNP (where PNP is bis((diethylphosphino)methyl)methylamine) have been prepared and isolated. These include cis-[Fe(PNP) 2(CH 3CN) 2](BF 4) 2 (3), cis-[Fe(PNP) 2(CH 3CN)(CO)](BF 4) 2 (4), trans-[Fe-(PNP)(dmpm)(CH 3CN) 2](BF 4) 2 (5), trans-Fe(PNP)(dmpm)Cl 2 (6), trans-[Fe(PNP)(dmpm) (CO)-Cl] 2[FeCl 4] (7), trans-HFe(PNP)(dmpm)Cl (8), and trans-[HFe(PNP)(dmpm)(CH 3CN)]BPh 4 (9) (where dmpm is bis(dimethylphosphino)methane). In addition, the cations trans-[HFe-(PNP)(dmpm) (CO)] + (10) and trans-[(H 2)Fe(PNP)(dmpm)(H)] + (11) have been observed in solution. These complexes all possess a pendant base that bridges the two phosphorus atoms of the PNP ligand. A cis geometry is observed for those complexes containing two PNP ligands, whereas a trans geometry is observed for the complexes containing one PNP ligand and one dmpm ligand. The molecular structures of cis-[Fe(PNP) 2(CH 3CN)(CO)](BPh 4) 2 and trans-[HFe(PNP)(dmpm) (CH 3CN)]BPh 4 have been confirmed by X-ray diffraction studies. Protonation of 5, 7, and 10 occurs at the nitrogen atom of the PNP ligand, and pK a values are reported for the corresponding protonated complexes. The formation of the dihydrogen complex [trans-[(H 2)Fe(PNP)(dmpm)(H)] + and the protonated PNHP complex trans-[HFe-(PNHP)(dmpm)(CO)] 2+ demonstrate that intramolecular heterolytic cleavage of the dihydrogen ligand can be controlled by varying the nature of the ligand trans to the incipient dihydrogen ligand.

AB - A series of cis and trans Fe(II) complexes containing the diphosphine ligand PNP (where PNP is bis((diethylphosphino)methyl)methylamine) have been prepared and isolated. These include cis-[Fe(PNP) 2(CH 3CN) 2](BF 4) 2 (3), cis-[Fe(PNP) 2(CH 3CN)(CO)](BF 4) 2 (4), trans-[Fe-(PNP)(dmpm)(CH 3CN) 2](BF 4) 2 (5), trans-Fe(PNP)(dmpm)Cl 2 (6), trans-[Fe(PNP)(dmpm) (CO)-Cl] 2[FeCl 4] (7), trans-HFe(PNP)(dmpm)Cl (8), and trans-[HFe(PNP)(dmpm)(CH 3CN)]BPh 4 (9) (where dmpm is bis(dimethylphosphino)methane). In addition, the cations trans-[HFe-(PNP)(dmpm) (CO)] + (10) and trans-[(H 2)Fe(PNP)(dmpm)(H)] + (11) have been observed in solution. These complexes all possess a pendant base that bridges the two phosphorus atoms of the PNP ligand. A cis geometry is observed for those complexes containing two PNP ligands, whereas a trans geometry is observed for the complexes containing one PNP ligand and one dmpm ligand. The molecular structures of cis-[Fe(PNP) 2(CH 3CN)(CO)](BPh 4) 2 and trans-[HFe(PNP)(dmpm) (CH 3CN)]BPh 4 have been confirmed by X-ray diffraction studies. Protonation of 5, 7, and 10 occurs at the nitrogen atom of the PNP ligand, and pK a values are reported for the corresponding protonated complexes. The formation of the dihydrogen complex [trans-[(H 2)Fe(PNP)(dmpm)(H)] + and the protonated PNHP complex trans-[HFe-(PNHP)(dmpm)(CO)] 2+ demonstrate that intramolecular heterolytic cleavage of the dihydrogen ligand can be controlled by varying the nature of the ligand trans to the incipient dihydrogen ligand.

UR - http://www.scopus.com/inward/record.url?scp=18844378104&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=18844378104&partnerID=8YFLogxK

U2 - 10.1021/om050071c

DO - 10.1021/om050071c

M3 - Article

AN - SCOPUS:18844378104

VL - 24

SP - 2481

EP - 2491

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 10

ER -