Diiron Dithiolate Hydrides Complemented with Proton‐Responsive Phosphine–Amine Ligands
Abstract
The reaction of Fe 2 (pdt)(CO) 6 with two equivalents of Ph 2 PC 6 H 4 NH 2 (PNH 2 ) affords the amido hydride HFe 2 (pdt)(CO) 2 (PNH 2 )(PNH) {[H 1 H] 0 , pdt 2– = CH 2 (CH 2 S – ) 2 }. Isolated intermediates in this conversion include Fe 2 (pdt)(CO) 5 (κ 1 ‐PNH 2 ) and Fe 2 (pdt)(CO) 4 (κ 2 ‐PNH 2 ). X‐ray crystallographic analysis of [H 1 H] 0 shows that the chelating amino/amido–phosphine ligands occupy trans ‐dibasal positions. The 31 P NMR spectrum indicates that [H 1 H] 0 undergoes rapid proton exchange between the amido and amine centers. No exchange was observed for the hydride. Protonation of [H 1 H] 0 gives [HFe 2 (pdt)(CO) 2 (PNH 2 ) 2 ] + ([H 2 1 H] + ), which contains two equivalent amino–phosphine ligands. Single‐crystal X‐ray crystallographic analysis of [H 2 1 H] + also reveals hydrogen bonds between the exo amine protons with a THF molecule and BF 4 . Deprotonation of [H 1 H] 0 with potassium tert ‐butoxide gave [HFe 2 (pdt)(CO) 2 (PNH) 2 ] – ([ 1 H] –more »
- Authors:
-
- School of Chemical Sciences University of Illinois at Urbana‐Champaign 61801 Urbana IL USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1400636
- Grant/Contract Number:
- DEFG02‐90ER14146
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- European Journal of Inorganic Chemistry
- Additional Journal Information:
- Journal Name: European Journal of Inorganic Chemistry Journal Volume: 2017 Journal Issue: 25; Journal ID: ISSN 1434-1948
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Carlson, Michaela R., Gilbert‐Wilson, Ryan, Gray, Danielle R., Mitra, Joyee, Rauchfuss, Thomas B., and Richers, Casseday P. Diiron Dithiolate Hydrides Complemented with Proton‐Responsive Phosphine–Amine Ligands. Germany: N. p., 2017.
Web. doi:10.1002/ejic.201700474.
Carlson, Michaela R., Gilbert‐Wilson, Ryan, Gray, Danielle R., Mitra, Joyee, Rauchfuss, Thomas B., & Richers, Casseday P. Diiron Dithiolate Hydrides Complemented with Proton‐Responsive Phosphine–Amine Ligands. Germany. https://doi.org/10.1002/ejic.201700474
Carlson, Michaela R., Gilbert‐Wilson, Ryan, Gray, Danielle R., Mitra, Joyee, Rauchfuss, Thomas B., and Richers, Casseday P. Wed .
"Diiron Dithiolate Hydrides Complemented with Proton‐Responsive Phosphine–Amine Ligands". Germany. https://doi.org/10.1002/ejic.201700474.
@article{osti_1400636,
title = {Diiron Dithiolate Hydrides Complemented with Proton‐Responsive Phosphine–Amine Ligands},
author = {Carlson, Michaela R. and Gilbert‐Wilson, Ryan and Gray, Danielle R. and Mitra, Joyee and Rauchfuss, Thomas B. and Richers, Casseday P.},
abstractNote = {The reaction of Fe 2 (pdt)(CO) 6 with two equivalents of Ph 2 PC 6 H 4 NH 2 (PNH 2 ) affords the amido hydride HFe 2 (pdt)(CO) 2 (PNH 2 )(PNH) {[H 1 H] 0 , pdt 2– = CH 2 (CH 2 S – ) 2 }. Isolated intermediates in this conversion include Fe 2 (pdt)(CO) 5 (κ 1 ‐PNH 2 ) and Fe 2 (pdt)(CO) 4 (κ 2 ‐PNH 2 ). X‐ray crystallographic analysis of [H 1 H] 0 shows that the chelating amino/amido–phosphine ligands occupy trans ‐dibasal positions. The 31 P NMR spectrum indicates that [H 1 H] 0 undergoes rapid proton exchange between the amido and amine centers. No exchange was observed for the hydride. Protonation of [H 1 H] 0 gives [HFe 2 (pdt)(CO) 2 (PNH 2 ) 2 ] + ([H 2 1 H] + ), which contains two equivalent amino–phosphine ligands. Single‐crystal X‐ray crystallographic analysis of [H 2 1 H] + also reveals hydrogen bonds between the exo amine protons with a THF molecule and BF 4 . Deprotonation of [H 1 H] 0 with potassium tert ‐butoxide gave [HFe 2 (pdt)(CO) 2 (PNH) 2 ] – ([ 1 H] – ), which was characterized spectroscopically. The complex has time‐averaged C 2 symmetry with two amido–phosphine ligands. FTIR spectroscopic measurements show that υ CO shifts by approximately 20 cm –1 in the series [ 1 H] – , [H 1 H] 0 , and [H 2 1 H] + . These shifts are comparable to those seen for the S‐protonation of the (NC) 2 (CO)Fe(µ‐Scys) 2 Ni(Scys) 2 site in the [NiFe]‐hydrogenases.},
doi = {10.1002/ejic.201700474},
journal = {European Journal of Inorganic Chemistry},
number = 25,
volume = 2017,
place = {Germany},
year = {Wed Jul 05 00:00:00 EDT 2017},
month = {Wed Jul 05 00:00:00 EDT 2017}
}
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