TY - JOUR
T1 - Redox and "antioxidant" Properties of Fe 2 (μ-SH) 2 (CO) 4 (PPh 3 ) 2
AU - Kagalwala, Husain N.
AU - Lalaoui, Noémie
AU - Li, Qian Li
AU - Liu, Liang
AU - Woods, Toby
AU - Rauchfuss, Thomas B.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/2/18
Y1 - 2019/2/18
N2 - The chemistry of Fe 2 (μ-SH) 2 (CO) 4 (PPh 3 ) 2 (2 HH ) is described with attention to S-S coupling reactions. Produced by the reduction of Fe 2 (μ-S 2 )(CO) 4 (PPh 3 ) 2 (2), 2 HH is an analogue of Fe 2 (μ-SH) 2 (CO) 6 (1 HH ), which exhibits well-behaved S-centered redox. Both 2 HH and the related 2 MeH exist as isomers that differ with respect to the stereochemistry of the μ-SR ligands (R = H, Me). Compounds 2 HH , 2 MeH , and 2 protonate to give rare examples of Fe-SH and Fe-S 2 hydrides. Salts of [H2] + , [H2 HH ] + , and [H2 MeH ] + were characterized crystallographically. Complex 2 HH reduces O 2 , H 2 O 2 , (PhCO 2 ) 2 , and Ph 2 N 2 , giving 2. Related reactions involving 1 HH gave uncharacterizable polymers. The differing behaviors of 2 HH and 1 HH reflect stabilization of the ferrous intermediates by the PPh 3 ligands. When independently generated by the reaction of 2 HH with 2,2,6,6-tetramethyl-1-piperidinyloxy, 2∗ quantitatively converts to 2 or, in the presence of C 2 H 4 , is trapped as the ethanedithiolate Fe 2 (μ-S 2 C 2 H 4 )(CO) 4 (PPh 3 ) 2 . Evidence is presented that the Hieber-Gruber synthesis of 1 involves polysulfido intermediates [Fe 2 (μ-S n ) 2 (CO) 6 ] 2- (n > 1). Two relevant experiments are as follows: (i) protonation of [Fe 4 (μ-S) 2 (μ-S 2 )CO) 12 ] 2- gives 1 and 1 HH , and (ii) oxidation of 1 HH by sulfur gives 1.
AB - The chemistry of Fe 2 (μ-SH) 2 (CO) 4 (PPh 3 ) 2 (2 HH ) is described with attention to S-S coupling reactions. Produced by the reduction of Fe 2 (μ-S 2 )(CO) 4 (PPh 3 ) 2 (2), 2 HH is an analogue of Fe 2 (μ-SH) 2 (CO) 6 (1 HH ), which exhibits well-behaved S-centered redox. Both 2 HH and the related 2 MeH exist as isomers that differ with respect to the stereochemistry of the μ-SR ligands (R = H, Me). Compounds 2 HH , 2 MeH , and 2 protonate to give rare examples of Fe-SH and Fe-S 2 hydrides. Salts of [H2] + , [H2 HH ] + , and [H2 MeH ] + were characterized crystallographically. Complex 2 HH reduces O 2 , H 2 O 2 , (PhCO 2 ) 2 , and Ph 2 N 2 , giving 2. Related reactions involving 1 HH gave uncharacterizable polymers. The differing behaviors of 2 HH and 1 HH reflect stabilization of the ferrous intermediates by the PPh 3 ligands. When independently generated by the reaction of 2 HH with 2,2,6,6-tetramethyl-1-piperidinyloxy, 2∗ quantitatively converts to 2 or, in the presence of C 2 H 4 , is trapped as the ethanedithiolate Fe 2 (μ-S 2 C 2 H 4 )(CO) 4 (PPh 3 ) 2 . Evidence is presented that the Hieber-Gruber synthesis of 1 involves polysulfido intermediates [Fe 2 (μ-S n ) 2 (CO) 6 ] 2- (n > 1). Two relevant experiments are as follows: (i) protonation of [Fe 4 (μ-S) 2 (μ-S 2 )CO) 12 ] 2- gives 1 and 1 HH , and (ii) oxidation of 1 HH by sulfur gives 1.
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U2 - 10.1021/acs.inorgchem.8b03344
DO - 10.1021/acs.inorgchem.8b03344
M3 - Article
C2 - 30724559
AN - SCOPUS:85062035801
SN - 0020-1669
VL - 58
SP - 2761
EP - 2769
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 4
ER -