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 language | English |
|---|---|
| Pages (from-to) | 2481-2491 |
| Number of pages | 11 |
| Journal | Organometallics |
| Volume | 24 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - May 9 2005 |
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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 journal › Article
}
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.
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U2 - 10.1021/om050071c
DO - 10.1021/om050071c
M3 - Article
VL - 24
SP - 2481
EP - 2491
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 10
ER -