Synthesis of a New Family of Heteronuclear Thiolate Iron Complexes that Contain Isocyanide Ligands

Chen, Pingping; Peng, Ying; Jia, Chunmei; Qü, Jingping

doi:10.1002/ejic.201000676

Cited by 16 publications

(4 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The Fe1–C27 bond length is 1.864(7) Å, and the Fe1–C27–N1 bond angle is 178.7(5)°, which are similar to reported iron complexes with an analogous slightly bent structural moiety . The C27N1 bond length of 1.143(7) Å is slightly shorter than that of the nitrogen–carbon triple bond length (1.157(5) Å), and close to those of thiolate-bridged diiron t BuNC complexes featuring Cp* [Cp*Fe(μ-1 κ 3 SSS’:2 κ 2 SS-tpdt){Cp*Fe-( t - t BuNC)}][PF 6 ] (1.148(8) Å), [Cp*Fe( t -SEt)(μ-SEt) 2 ( t - t BuCN)FeCp*] (1.155(5) Å), [Cl 2 Fe(μ-SEt) 2 ( t - t BuCN)FeCp*] (1.149(5) Å), and some heteronuclear complexes with {Cp*Fe( t BuNC)} fragment …”

Section: Resultsmentioning

confidence: 99%

“…(1.155(5) Å), 21 [Cl 2 Fe(μ-SEt) 2 (t-t BuCN)FeCp*] (1.149(5) Å), 21 and some heteronuclear complexes with {Cp*Fe-( t BuNC)} fragment. 22 Next, we examined the reactivity of azide, which can also play as a substrate of nitrogenase to be transformed into N 2 , NH 3 , or N 2 H 4 . 2,23 As illustrated in Scheme 1, the reactivity of hydride complexes toward organic substituted azide TMSN 3 was investigated as a model reaction.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Reactivity toward Unsaturated Small Molecules of Thiolate-Bridged Diiron Hydride Complexes

Yang

Zhang

et al. 2018

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

In the presence of 1 equiv of t BuNC, the homolytic cleavage of the Fe III −H bond in the diiron terminal hydride complex [Cp*Fe(t-H)(μ-) smoothly took place to release 1/2 H 2 , followed by binding of a t BuNC group to the unsaturated Fe II center. Interestingly, upon exposure of 1[BF 4 ] to 1 atm of acetylene, the isomerization process of the hydride ligand from the terminal to bridging coordination site was unaffected. Upon treatment of the diiron hydride bridged complex 2[BF 4 ] with acetylene at 30 °C, two Fe III −H bonds were broken, and then an acetylene molecule was coordinated to the diiron centers in a novel μ-η 2 :η 2 side-on fashion. In the above reaction system, the hydride ligands whether terminal or bridging all play a role as the electron donor for the reduction of the diiron centers from Fe III Fe III to Fe III Fe II . These reaction patterns are reminiscent of the vital E 4 state responsible for N 2 binding and H 2 liberation in the catalytic cycle of nitrogenase, which contains two {Fe−H−Fe} motifs as electron reservoirs for the reduction of the iron centers. Differently, when treating 1[BF 4 ] with TMSN 3 , the terminal hydride ligand was inserted into the azide group to give a diiron amide complex 4[BF 4 ] in moderate yield.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Reactivity toward Unsaturated Small Molecules of Thiolate-Bridged Diiron Hydride Complexes

Yang

Zhang

et al. 2018

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…For a structural comparision with [ClPt(-dppm) 2 (-C NMe)Ni(CNMe)]Cl, see Ratliff et al (1990). For a structural comparision with [Cp*FeCNPh(-C NPh)(-SEt)PdCl(PPh 3 )]PF 6 , see Chen et al (2010). For a structural comparision with [(EtNC) 3 Fe(-C NEt) 3 Fe(CNEt) 3 ], see Basset et al (1981).…”

Section: Related Literaturementioning

confidence: 99%

[μ-Bis(diphenylphosphanyl)methane]tricarbonyl(μ-p-toluenesulfonylmethyl isocyanato)(triphenylphosphane)ironplatinum(Fe—Pt)

et al. 2012

View full text Add to dashboard Cite

The title compound, [FePt(C9H9NO2S)(C18H15P)(C25H22P2)(CO)3], represents a rare example of an isonitrile-bridged heterobimetallic complex (here Pt and Fe) and is an interesting precursor for the preparation of heterodinuclear μ-aminocarbyne complexes, since the basic imine-type N atom of the μ2-C=N–R ligand readily undergoes addition with various electrophiles to afford iminium-like salts. In the crystal, the almost symmetrically bridging μ2-C=N-R ligand (neglecting the different atomic radii of Fe and Pt) is strongly bent towards the Fe(CO)3 fragment, with a C=N-R angle of only 121.1 (4)°.

show abstract

“…Coordination, activation, and catalytic conversion of various small molecules by synthetic diiron complexes bearing thiolate and Cp* ligands is one of the research fields in our group 12–14. In our previous work, we obtained several [NiFe] and [FePd] heterodimetallic complexes containing the Cp*Fe fragment 13. Recently, we prepared a diiron nitrogenase model complex [Cp*Fe(μ‐bdt)FeCp*] (bdt = benzene‐1,2‐dithiolate) that can realize the conversion of hydrazine into ammonia along the pathway: HN=NH → HN–NH 2 → NH 2 → NH 3 14.…”

Section: Introductionmentioning

confidence: 99%

Versatile Reactivity of CH₃CN‐Coordinated Nickel‐Iron Heterodimetallic Complexes with Cp* Ligand on Diazadithiolate (N₂S₂) or Dithiadithiolate (S₄) Platforms

Yang

et al. 2015

Eur J Inorg Chem

Self Cite

View full text Add to dashboard Cite

By using 3,7‐dithianonane‐1,9‐dithiol (S4) and N,N′‐dimethyl‐N,N′‐bis(2‐mercaptoethyl)ethylenediamine (N2S2) as ligands, two CH3CN‐coordinated nickel‐iron heterodimetallic complexes, [NiS4Fe(CH3CN)Cp*][PF6] (1a) and [NiN2S2Fe(CH3CN)Cp*][PF6] (1b) (Cp* = η5‐C5Me5), were synthesized and characterized spectroscopically and crystallographically. Reactivities of 1a and 1b towards CO, CH2Cl2, HBF4, and NOPF6 have also been investigated. A series of complexes coordinated with small molecules [NiS4Fe(L)Cp*][PF6]n [n = 1, L = Cl (2a), CO (3a); n = 2, L = NO (4a)], [NiN2S2Fe(L)Cp*][PF6] [L = Cl (2b), CO (3b)] were obtained. We also studied the redox properties of 2a, 2b, 3a, and 3b by cyclic voltammetry in CH2Cl2 and in CH3CN solution. Complex 3a was found to be an excellent electrocatalyst for proton reduction from HBF4.

show abstract

Synthesis of a New Family of Heteronuclear Thiolate Iron Complexes that Contain Isocyanide Ligands

Cited by 16 publications

References 53 publications

Reactivity toward Unsaturated Small Molecules of Thiolate-Bridged Diiron Hydride Complexes

Reactivity toward Unsaturated Small Molecules of Thiolate-Bridged Diiron Hydride Complexes

[μ-Bis(diphenylphosphanyl)methane]tricarbonyl(μ-p-toluenesulfonylmethyl isocyanato)(triphenylphosphane)ironplatinum(Fe—Pt)

Versatile Reactivity of CH₃CN‐Coordinated Nickel‐Iron Heterodimetallic Complexes with Cp* Ligand on Diazadithiolate (N₂S₂) or Dithiadithiolate (S₄) Platforms

Contact Info

Product

Resources

About

Synthesis of a New Family of Heteronuclear Thiolate Iron Complexes that Contain Isocyanide Ligands

Cited by 16 publications

References 53 publications

Reactivity toward Unsaturated Small Molecules of Thiolate-Bridged Diiron Hydride Complexes

Reactivity toward Unsaturated Small Molecules of Thiolate-Bridged Diiron Hydride Complexes

[μ-Bis(diphenylphosphanyl)methane]tricarbonyl(μ-p-toluenesulfonylmethyl isocyanato)(triphenylphosphane)ironplatinum(Fe—Pt)

Versatile Reactivity of CH3CN‐Coordinated Nickel‐Iron Heterodimetallic Complexes with Cp* Ligand on Diazadithiolate (N2S2) or Dithiadithiolate (S4) Platforms

Contact Info

Product

Resources

About

Versatile Reactivity of CH₃CN‐Coordinated Nickel‐Iron Heterodimetallic Complexes with Cp* Ligand on Diazadithiolate (N₂S₂) or Dithiadithiolate (S₄) Platforms