PMID- 29188999
OWN - NLM
STAT- MEDLINE
DCOM- 20180228
LR  - 20180228
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 56
IP  - 24
DP  - 2017 Dec 18
TI  - Studies on Chemical Reactivity and Electrocatalysis of Two 
      Acylmethyl(hydroxymethyl)pyridine Ligand-Containing [Fe]-Hydrogenase Models 
      (2-COCH(2)-6-HOCH(2)C(5)H(3)N)Fe(CO)(2)L (L = eta(1)-SCOMe, eta(1)-2-SC(5)H(4)N).
PG  - 15216-15230
LID - 10.1021/acs.inorgchem.7b02582 [doi]
AB  - On the basis of preparation and characterization of [Fe]-H(2)ase models 
      (2-COCH(2)-6-HOCH(2)C(5)H(3)N)Fe(CO)(2)L (A, L = eta(1)-SCOMe; B, L = 
      eta(1)-2-SC(5)H(4)N), the chemical reactivities of A and B with various 
      electrophilic and nucleophilic reagents have been investigated, systematically. 
      Thus, when A reacted with 1 equiv of MeCOCl in the presence of Et(3)N in MeCN to 
      give the eta(2)-SCOMe-coordinated acylation product 
      (2-COCH(2)-6-MeCO(2)CH(2)C(5)H(3)N)Fe(CO)(2)(eta(2)-SCOMe) (1), treatment of A with 
      excess HBF(4).Et(2)O in MeCN gave the cationic MeCN-coordinated complex 
      [(2-COCH(2)-6-HOCH(2)C(5)H(3)N)Fe(CO)(2)(MeCN)](BF(4)) (2). In addition, when 2 
      was treated with 1 equiv of 2,6-(p-4-MeC(6)H(4))(2)C(6)H(3)SK or PPh(3) in 
      CH(2)Cl(2) to give the thiophenolato- and PPh(3)-substituted derivatives 
      (2-COCH(2)-6-HOCH(2)C(5)H(3)N)Fe(CO)(2)[2,6-(p-MeC(6)H(4))(2)C(6)H(3)S] (3) and 
      [(2-COCH(2)-6-HOCH(2)C(5)H(3)N)Fe(CO)(2)(PPh(3))](BF(4)) (4), treatment of B with 
      1 equiv of PMe(3) or P(OMe)(3) in THF afforded the phosphine- and 
      phosphite-substituted complexes 
      (2-COCH(2)-6-HOCH(2)C(5)H(3)N)(eta(1)-2-SC(5)H(4)N)Fe(CO)(2)L (5, L = PMe(3); 6, L 
      = P(OMe)(3)). Interestingly, in contrast to A, when B reacted with excess 
      HBF(4).Et(2)O in MeCN to afford the BF(3) adduct 
      [2-COCH(2)-6-HO(BF(3))CH(2)C(5)H(3)N]Fe(CO)(2)(eta(1)-2-SC(5)H(4)N) (7), reaction 
      of B with 1 equiv of p-MeC(6)H(4)COCl in the presence of Et(3)N in MeCN gave not 
      only the expected 2-acylmethyl-6-p-toluoyloxomethylpyridine-containing complex 
      (2-COCH(2)-6-p-MeC(6)H(4)CO(2)CH(2)C(5)H(3)N)Fe(CO)(2)(eta(2)-2-SC(5)H(4)N) (8), 
      but also gave the unexpected 
      2-toluoyloxovinyl-6-toluoyloxomethylpyridine-containing complex 
      (2-p-MeC(6)H(4)CO(2)C(2)H-6-p-MeC(6)H(4)CO(2)CH(2)C(5)H(3)N)Fe(CO)(2)(eta(2)-2-SC(5)H(4)N) 
      (9). While the possible pathways for the novel reactions leading to complexes 1, 
      2, and 7-9 are suggested, the structures of complexes B, 1-4, and 6-9 were 
      unambiguously confirmed by X-ray crystallography. In addition, model complexes A 
      and B have been found to be catalysts for proton reduction to H(2) from TFA under 
      CV conditions.
FAU - Song, Li-Cheng
AU  - Song LC
AUID- ORCID: 0000-0003-0964-8869
AD  - Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, 
      College of Chemistry, and double daggerCollaborative Innovation Center of Chemical Science 
      and Engineering (Tianjin), Nankai University , Tianjin 300071, China.
FAU - Zhu, Liang
AU  - Zhu L
AD  - Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, 
      College of Chemistry, and double daggerCollaborative Innovation Center of Chemical Science 
      and Engineering (Tianjin), Nankai University , Tianjin 300071, China.
FAU - Hu, Fu-Qiang
AU  - Hu FQ
AD  - Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, 
      College of Chemistry, and double daggerCollaborative Innovation Center of Chemical Science 
      and Engineering (Tianjin), Nankai University , Tianjin 300071, China.
FAU - Wang, Yong-Xiang
AU  - Wang YX
AD  - Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, 
      College of Chemistry, and double daggerCollaborative Innovation Center of Chemical Science 
      and Engineering (Tianjin), Nankai University , Tianjin 300071, China.
LA  - eng
PT  - Journal Article
DEP - 20171130
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
RN  - 0 (Iron Compounds)
RN  - 0 (Iron-Sulfur Proteins)
RN  - 0 (Ligands)
RN  - 0 (Protons)
RN  - 0 (Pyridines)
RN  - 0 (acylmethyl(hydroxymethyl)pyridine)
RN  - EC 1.12.- (iron hydrogenase)
RN  - EC 1.12.7.2 (Hydrogenase)
SB  - IM
MH  - Biomimetic Materials/*chemistry
MH  - Catalysis
MH  - Crystallography, X-Ray
MH  - Electrochemical Techniques
MH  - Hydrogenase/*chemistry
MH  - Iron Compounds/*chemistry
MH  - Iron-Sulfur Proteins/*chemistry
MH  - Ligands
MH  - Models, Molecular
MH  - Oxidation-Reduction
MH  - Protons
MH  - Pyridines/*chemistry
EDAT- 2017/12/01 06:00
MHDA- 2018/03/01 06:00
CRDT- 2017/12/01 06:00
PHST- 2017/12/01 06:00 [pubmed]
PHST- 2018/03/01 06:00 [medline]
PHST- 2017/12/01 06:00 [entrez]
AID - 10.1021/acs.inorgchem.7b02582 [doi]
PST - ppublish
SO  - Inorg Chem. 2017 Dec 18;56(24):15216-15230. doi: 10.1021/acs.inorgchem.7b02582. 
      Epub 2017 Nov 30.