Syntheses of Novel Fe/S Clusters with μ‐Aminocarbyne Ligands

Shi, Yao‐Cheng; Fu, Qiang

doi:10.1002/zaac.201300192

Cited by 16 publications

(6 citation statements)

References 35 publications

(35 reference statements)

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“…Bridging sulfides are the key to the aggregation and the stabilization of the final metal scaffold. Possible aminocarbyne precursors are dimethylthiocarbamoyl chloride ClC(=S)NMe2 [184], tetramethylthiourea (NMe2)2CS 66 [185], dialkyldithiocarbamates and related species [186,187,188,189,190]. All of these reactions usually show a limited/poor selectivity.…”

Section: Thermal Reactions Of [M3(comentioning

confidence: 99%

Aminocarbyne ligands in organometallic chemistry

Biancalana

Marchetti

2021

Coordination Chemistry Reviews

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Section: Thermal Reactions Of [M3(comentioning

confidence: 99%

Aminocarbyne ligands in organometallic chemistry

Biancalana

Marchetti

2021

Coordination Chemistry Reviews

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“…Analogous bis‐aminoalkylidyne species were also reported in the past . On the other hand, stable polynuclear compounds with bridging aminoalkylidyne ligands are relatively rare in the literature, based on molybdenum, nickel, tungsten, platinum, iron and heterodinuclear systems, and their chemistry has been sparingly developed.…”

Section: Introductionmentioning

confidence: 99%

Constructing Organometallic Architectures from Aminoalkylidyne Diiron Complexes

Marchetti

2018

Eur J Inorg Chem

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The chemistry of diiron complexes has seen a recent renaissance, due to the prominent role played by the element iron in the development of sustainable synthetic processes and the cooperative effects provided by two metal centers working in concert, that is a concept amazingly exploited by Nature. Aminoalkylidyne derivatives of [Fe 2 Cp 2 (CO) 4 ] are a convenient scaffold to grow organic fragments; in particular, the facile re-[a] received his PhD degree in Chemistry from the University of Bologna in 2003, then he moved to the University of Pisa in 2006, where he is currently Professor of Inorganic Chemistry. He has co-authored over 150 papers in international journals, dealing with several aspects of the coordination chemistry of transition metal compounds. He was awarded the Nasini Prize by the Italian Chemical Society in 2014, for his contribution to the chemistry of group 5 and 6 metal compounds and to the exploration of unconventional modes of metal mediated C-C bond formation. 3990 Scheme 7. Coupling of isocyanide ligands promoted by acetylide addition to aminoalkylidyne complexes. (a) R = Xyl, R′ = Ph; R = Xyl, R′ = 4-C 6 H 4 Me; R = Me, R′ = Ph. (b) γ-Al 2 O 3 , R′ = SiMe 3 . [51]Eur. 3991Scheme 8. Base-assisted coupling of aminoalkylidyne ligand (R = Me, Xyl or 4-C 6 H 4 OMe) with (a) alkenes (R′ = H, R′′ = CN, CO 2 Me, Ph; R′ = R′′ = CO 2 Et) [53] and (b) allenes (R′ = R′′ = Me; R′ = Me, CO 2 Et, R′′ = H). [54] Scheme 9. Synthesis of vinyliminium complexes via alkyne insertion into Fe-μ-carbyne bond. Inset: possible forms of isomerism. [61][62][63] Eur.

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“…[ VII ] − and X belong to a general class of metal carbonyl clusters in which two M 2 units, each containing a metal–metal bond, are bound to a central main-group atom, a well-known configuration (Figure ). − Both [ VII ] − and X contain three Fe atoms and one Mn atom divided between two M 2 fragments (Figures and ). [ VII ] − and X each possess an MnFe(CO) 8 fragment as well as a diiron unit which is (μ-H)Fe 2 (CO) 6 (μ-CO) − and Fe 2 (CO) 8 for [ VII ] − and X , respectively.…”

Section: Resultsmentioning

confidence: 99%

“…X is a neutral molecule and obeys the 18-electron rule. The average M–M bond is 2.821(25) Å, similar to 2.816(44) Å, the average M–M bond distance for a variety of spirocyclic EM 2 (CO) 8 compounds where M were first-row transition metals. ,− It was also similar to the 2.8191(15) Å observed in [ VII ] − . Table gives a comparison of X to all known E{Fe 2 (CO) 8 } 2 clusters where E is a main-group atom (E = Si, Ge, In, Sn, Pb).…”

Section: Resultsmentioning

confidence: 99%

Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et₄N]₂[HAs{Fe(CO)₄}₃] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials

2016

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The chemistry of [Et 4 N] 2 [HAs{Fe(CO) 4 } 3 ] ([Et 4 N] 2 [I]) has been explored with the goal of preparing heterometallic compounds for use as single-source precursors to metal pnictide phases. Reaction of AgPF 6 with [Et 4 N] 2 [I] in THF produces [Et 4 N][HAs{Fe 2 (CO) 6 (μ-CO)(μ-H)}{Fe-(CO) 4 }] in 12% yield, but the yield is improved to 71% if the reaction is carried out with added [Et 4 N][HFe(CO) 4 ]. The structure possesses rare As−H and {Fe 2 (CO) 6 (μ-CO)(μ-H)} fragments. The addition of [CPh 3 ][BF 4 ] to [Et 4 N] 2 [I] in THF gives [Et 4 N][Fe 3 (CO) 9 (μ-CO){μ 3 -AsFe(CO) 4 }] in 45% yield. This compound is also obtained as a minor product from oxidation of [Et 4 N] 2 [I] with 1 equiv of AgPF 6, AsCl 3, SbCl 3 , or BiCl 3 in THF. The cluster consists of an Fe 3 As tetrahedron with an isolated Fe(CO) 4 unit bound to the arsenic in a spikedtetrahedral arrangement. Refluxing [Et 4 N] 2 [I] with 1 equiv of AgPF 6 in THF produces [Et 4 N][(μ-H) 2 Fe 3 (CO) 9 ){μ 3 -AsFe(CO) 4 }]. This cluster is similar to [Et 4 N][Fe 3 (CO) 9 (μ-CO){μ 3 -AsFe(CO) 4 }] with the bridging CO being replaced by two bridging hydride ligands. Treatment of [Et 4 N] 2 [I] with 1 equiv of Mn(CO) 5 Br in THF gives the spirocyclic compound [Et 4 N][{FeMn(CO) 8 }(μ 4 -As){Fe 2 (CO) 6 (μ-CO)(μ-H)}] in 52% yield. Refluxing this cluster in the presence of triethylamine and an additional 1.8 equiv of Mn(CO) 5 Br gives [Et 4 N][Fe 3 (CO) 9 (μ-CO){μ 3 -AsMn(CO) 4 Br-cis}] in low yield. Alternatively, treating [Et 4 N][{FeMn(CO) 8 }(μ 4 -As){Fe 2 (CO) 6 (μ-CO)(μ-H)}] with triflic acid or an oxidant ([Ox] = Cu + , Ag + , Cu 2+ , CPh 3 + ) in dichloromethane produces the two neutral compounds (μ-H) 2 Fe 3 (CO) 9 {μ 3 -AsMn(CO) 5 } and {FeMn(CO) 8 }(μ 4 -As){Fe 2 (CO) 8 } in trace amounts and high yield, respectively. The former could be removed by treatment with base in nonpolar solvents. Neutral {FeMn(CO) 8 }(μ 4 -As){Fe 2 (CO) 8 } can then be isolated by filtration and evaporation in 74% yield. An improved synthesis of the known [Fe 3 (CO) 9 (μ-CO){μ 3 -PFe(CO) 4 }] − as its tetraethylammonium salt is also included. All compounds were characterized by spectroscopy, by ESI-mass spectrometry, and by single-crystal X-ray diffraction.

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Syntheses of Novel Fe/S Clusters with μ‐Aminocarbyne Ligands

Abstract: Abstract. The reaction of Fe 3 (CO) 12 with (C 3 H 5 ) 2 NCS 2 K in THF at room temperature afforded a red-brown solution. Treatment of the thus-obtained solution with MeI and PhCH 2 Br afforded clusters 1, (μ-MeS)Fe 2 (CO) 6 (μ 4 -S)Fe 2 (CO) 6 (μ-CN(C 3 H 5 ) 2 ),

Cited by 16 publications

References 35 publications

Aminocarbyne ligands in organometallic chemistry

Aminocarbyne ligands in organometallic chemistry

Constructing Organometallic Architectures from Aminoalkylidyne Diiron Complexes

Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et₄N]₂[HAs{Fe(CO)₄}₃] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials

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Syntheses of Novel Fe/S Clusters with μ‐Aminocarbyne Ligands

Abstract: Abstract. The reaction of Fe 3 (CO) 12 with (C 3 H 5 ) 2 NCS 2 K in THF at room temperature afforded a red-brown solution. Treatment of the thus-obtained solution with MeI and PhCH 2 Br afforded clusters 1, (μ-MeS)Fe 2 (CO) 6 (μ 4 -S)Fe 2 (CO) 6 (μ-CN(C 3 H 5 ) 2 ),

Cited by 16 publications

References 35 publications

Aminocarbyne ligands in organometallic chemistry

Aminocarbyne ligands in organometallic chemistry

Constructing Organometallic Architectures from Aminoalkylidyne Diiron Complexes

Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et4N]2[HAs{Fe(CO)4}3] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials

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Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et₄N]₂[HAs{Fe(CO)₄}₃] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials