Synthesis and structure of dithiodiiron heptacarbonyl

Nametkin, N. S.; Kolobkov, B. I.; Tyurin, V. D.; Muratov, A. N.; Nekhaev, A. I.; Mavlonov, M.; Sideridu, A. Ya.; Александров, Г. Г.; Lebedev, A. V.; Tashev, M. T.; Dustov, H.B.

doi:10.1016/0022-328x(84)80661-0

Cited by 33 publications

(19 citation statements)

References 9 publications

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“…Interestingly, we detected significant amounts of a thermostable, vaporizable iron-carbonyl compound by GC-MS: (CO) 3 Fe=(OCS 2 )=Fe(CO) 3 , which contains two (CO) 3 Fe groups that are connected to each other by one single FeÀ Fe bond and by a dithiocarbonate group forming two Fe À S À Fe bridges. [39] The catalytic effects of the bio-organic products: We have established the formation of fundamental bio-organic compounds (a-amino acids, a-hydroxy acids, and their derivatives) using organo-metal chemistry under volcanic hydrothermal conditions; these reactions proceeded in the ligand sphere of cyano complexes of transition metals in the iron group with catalytic activities following the order Ni @ Co > Fe. From now on, these reactions will be termed "source reactions".…”

Section: Tetracyanonickelatementioning

confidence: 99%

Elements of Metabolic Evolution

Huber

Kraus

Hanzlik

et al. 2012

Chemistry A European J

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Research into the origin of evolution is polarized between a genetics-first approach, with its focus on polymer replication, and a metabolism-first approach that takes aim at chemical reaction cycles. Taking the latter approach, we explored reductive carbon fixation in a volcanic hydrothermal setting, driven by the chemical potential of quenched volcanic fluids for converting volcanic C1 compounds into organic products by transition-metal catalysts. These catalysts are assumed to evolve by accepting ever-new organic products as ligands for enhancing their catalytic power, which in turn enhances the rates of synthetic pathways that give rise to ever-new organic products, with the overall effect of a self-expanding metabolism. We established HCN, CO, and CH(3)SH as carbon nutrients, CO and H(2) as reductants, and iron-group transition metals as catalysts. In one case, we employed the "cyano-system" [Ni(OH)(CN)] with [Ni(CN)(4)](2-) as the dominant nickel-cyano species. This reaction mainly produced α-amino acids and α-hydroxy acids as well as various intermediates and derivatives. An organo-metal-catalyzed mechanism is suggested that mainly builds carbon skeletons by repeated cyano insertions, with minor CO insertions in the presence of CO. The formation of elemental nickel (Ni(0)) points to an active reduced-nickel species. In another case, we employed the mercapto-carbonyl system [Co(2)(CO)(8)]/Ca(OH)(2)/CO for the double-carbonylation of mercaptans. In a "hybrid system", we combined benzyl mercaptan with the cyano system, in which [Ni(OH)(CN)] was the most productive for the double-carbon-fixation reaction. Finally, we demonstrated that the addition of products of the cyano system (Gly, Ala) to the hybrid system increased productivity. These results demonstrate the chemical possibility of metabolic evolution through rate-promotion of one synthetic reaction by the products of another.

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Section: Tetracyanonickelatementioning

confidence: 99%

Elements of Metabolic Evolution

Huber

Kraus

Hanzlik

et al. 2012

Chemistry A European J

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“…[23] Each silicon atom in 3 shares three valence electrons with the Fe 2 (CO) 6 fragment through aS i ÀFe covalent bond and aS i ÀFe donor-acceptor bond. [24] With the valence electrons contributed from the carbene ligands,the Si[m-Fe 2 (CO) 6 ](m-CO)Si core in 3 is isoelectronic to the inorganic core in RP[m-Fe 2 (CO) 6 ](m-CO)PR [R = N(Pr i ) 2 (5), [25] Scheme 1] and S[m-Fe 2 (CO) 6 ](m-CO)S (6) [26] (Scheme 1). [19] However,t hey are obviously shorter than the reported iron-silyl bonds (2.493 , av) in cis-[Fe-(xantsil)(CO) 4 ].…”

Section: Methodsmentioning

confidence: 99%

“…[19] However,t hey are obviously shorter than the reported iron-silyl bonds (2.493 , av) in cis-[Fe-(xantsil)(CO) 4 ]. [24] With the valence electrons contributed from the carbene ligands,the Si[m-Fe 2 (CO) 6 ](m-CO)Si core in 3 is isoelectronic to the inorganic core in RP[m-Fe 2 (CO) 6 ](m-CO)PR [R = N(Pr i ) 2 (5), [25] Scheme 1] and S[m-Fe 2 (CO) 6 ](m-CO)S (6) [26] (Scheme 1). TheFe À Fe bond in 3 [2.6658 (8) ] is about 0.08 shorter than that of 3-Me (2.739 ).…”

mentioning

confidence: 99%

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

et al. 2015

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Reaction of carbene-stabilized disilicon (1) with Fe(CO)5 gives the 1:1 adduct L:Si=Si[Fe(CO)4 ]:L (L:=C{N(2,6-Pr(i) 2 C6 H3 )CH}2 ) (2) at room temperature. At raised temperature, however, 2 may react with another equivalent of Fe(CO)5 to give L:Si[μ-Fe2 (CO)6 ](μ-CO)Si:L (3) through insertion of both CO and Fe2 (CO)6 into the Si2 core, which represents the first experimental realization of transition metal-carbonyl-mediated cleavage of a Si=Si double bond. The structures and bonding of both 2 and 3 have been investigated by spectroscopic, crystallographic, and computational methods.

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“…However, they are obviously shorter than the reported iron–silyl bonds (2.493 Å, av) in cis ‐[Fe(xantsil)(CO) 4 ] 24. With the valence electrons contributed from the carbene ligands, the Si[μ‐Fe 2 (CO) 6 ](μ‐CO)Si core in 3 is isoelectronic to the inorganic core in RP[μ‐Fe 2 (CO) 6 ](μ‐CO)PR [R=N(Pr i ) 2 ( 5 ),25 Scheme ] and S[μ‐Fe 2 (CO) 6 ](μ‐CO)S ( 6 )26 (Scheme ). The FeFe bond in 3 [2.6658(8) Å] is about 0.08 Å shorter than that of 3‐Me (2.739 Å) 17.…”

Section: Methodsmentioning

confidence: 99%

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

et al. 2015

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Reaction of carbene‐stabilized disilicon (1) with Fe(CO)5 gives the 1:1 adduct L:SiSi[Fe(CO)4]:L (L:=C{N(2,6‐Pri2C6H3)CH}2) (2) at room temperature. At raised temperature, however, 2 may react with another equivalent of Fe(CO)5 to give L:Si[μ‐Fe2(CO)6](μ‐CO)Si:L (3) through insertion of both CO and Fe2(CO)6 into the Si2 core, which represents the first experimental realization of transition metal‐carbonyl‐mediated cleavage of a SiSi double bond. The structures and bonding of both 2 and 3 have been investigated by spectroscopic, crystallographic, and computational methods.

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Synthesis and structure of dithiodiiron heptacarbonyl

Cited by 33 publications

References 9 publications

Elements of Metabolic Evolution

Elements of Metabolic Evolution

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

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