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231224s2013 xx ||||| 00| ||eng c |
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|a pubmed24n1628.xml
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|a (DE-627)NLM230447406
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|a (NLM)23990692
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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| 100 |
1 |
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|a Bichler, Bernhard
|e verfasserin
|4 aut
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|a Heterolytic Cleavage of Dihydrogen by an Iron(II) PNP Pincer Complex via Metal-Ligand Cooperation
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|c 2013
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|a Text
|b txt
|2 rdacontent
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|a ohne Hilfsmittel zu benutzen
|b n
|2 rdamedia
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| 338 |
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|a Band
|b nc
|2 rdacarrier
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|a Date Revised 11.12.2024
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|a published: Print-Electronic
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|a Citation Status PubMed-not-MEDLINE
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|a The bis-carbonyl Fe(II) complex trans-[Fe(PNP-iPr)(CO)2Cl]+ reacts with Zn as reducing agent under a dihydrogen atmosphere to give the Fe(II) hydride complex cis-[Fe(PNP-iPr)(CO)2H]+ in 97% isolated yield. A crucial step in this reaction seems to be the reduction of the acidic NH protons of the PNP-iPr ligand to afford H2 and the coordinatively unsaturated intermediate [Fe(PNPH-iPr)(CO)2]+ bearing a dearomatized pyridine moiety. This species is able to bind and heterolytically cleave H2 to give cis-[Fe(PNP-iPr)(CO)2H]+. The mechanism of this reaction has been studied by DFT calculations. The proposed mechanism was supported by deuterium labeling experiments using D2 and the N-deuterated isotopologue of trans-[Fe(PNP-iPr)(CO)2Cl]+. While in the first case deuterium was partially incorporated into both N and Fe sites, in the latter case no reaction took place. In addition, the N-methylated complex trans-[Fe(PNPMe-iPr)(CO)2Cl]+ was prepared, showing no reactions with Zn and H2 under the same reaction conditions. An alternative synthesis of cis-[Fe(PNP-iPr)(CO)2H]+ was developed utilizing the Fe(0) complex [Fe(PNP-iPr)(CO)2]. This compound is obtained in high yield by treatment of either trans-[Fe(PNP-iPr)(CO)2Cl]+ or [Fe(PNP-iPr)Cl2] with an excess of NaHg or a stoichiometric amount of KC8 in the presence of carbon monoxide. Protonation of [Fe(PNP-iPr)(CO)2] with HBF4 gave the hydride complex cis-[Fe(PNP-iPr)(CO)2H]+. X-ray structures of both cis-[Fe(PNP-iPr)(CO)2H]+ and [Fe(PNP-iPr)(CO)2] are presented
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|a Journal Article
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|a Holzhacker, Christian
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Stöger, Berthold
|e verfasserin
|4 aut
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| 700 |
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|a Puchberger, Michael
|e verfasserin
|4 aut
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| 700 |
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|a Veiros, Luis F
|e verfasserin
|4 aut
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| 700 |
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|a Kirchner, Karl
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Organometallics
|d 1998
|g 32(2013), 15 vom: 12. Aug., Seite 4114-4121
|w (DE-627)NLM098167103
|x 0276-7333
|7 nnns
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| 773 |
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|g volume:32
|g year:2013
|g number:15
|g day:12
|g month:08
|g pages:4114-4121
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| 912 |
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|a GBV_USEFLAG_A
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| 912 |
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|a SYSFLAG_A
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| 912 |
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|a GBV_NLM
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| 912 |
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|a GBV_ILN_350
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|a AR
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| 952 |
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|d 32
|j 2013
|e 15
|b 12
|c 08
|h 4114-4121
|