Übergangsmetall-silyl-komplexe

Reinhard, G.; Hirle, Brigitte; Schubert, Ulrich

doi:10.1016/0022-328x(92)83083-t

Cited by 36 publications

(9 citation statements)

References 10 publications

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“…Our desire to explore the chemistry of borylene complexes of the heavier Group 8 metals was inspired by the observation that treatment of the iron metallate salt K[Fe(CO) 3 (PMe 3 )(SiR 3 )] with bulky aryldihaloboranes leads in some cases to terminal borylene complexes (Figure , top) . In preliminary work, we found that ruthenium analogues of this iron metallate salt could be prepared in a similar manner . These salts could be reacted in situ with aryldihaloboranes to form a range of products.…”

Section: Figurementioning

confidence: 99%

“…[3] In preliminary work,w ef ound that ruthenium analogues of this iron metallate salt could be prepared in asimilar manner. [10] These salts could be reacted in situ with aryldihaloboranes to form ar ange of products. Similart ot he Fe case, these reactions led in some cases to borylene products; however,t he mechanisms and the products were found to be distinctly different than those featuring iron.…”

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confidence: 99%

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Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation

Braunschweig

Damme

Dewhurst

et al. 2016

Chemistry A European J

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The reaction of the salts K[Ru(CO)3 (PMe3 )(SiR3 )] (R=Me, Et) with Br2 BDur or Cl2 BDur (Dur=2,3,5,6-Me4 C6 H) leads to both boryl and borylene complexes of divalent ruthenium, the former through simple salt elimination and the latter through subsequent CO loss and 1,2-halide shift. The balance of products can be altered by varying the reaction conditions; boryl complexes can be favored by the addition of CO, and borylene complexes by removal of CO under vacuum. All of these products are in competition with the corresponding (aryl)(halo)(trialkylsilyl)borane, a reductive elimination product. The Ru(II) borylene products and the mechanisms that form them are distinctly different from the analogous reactions with iron, which lead to low-valent borylene complexes, highlighting fundamental differences in oxidation state preferences between iron and ruthenium.

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Section: Figurementioning

confidence: 99%

mentioning

confidence: 99%

Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation

Braunschweig

Damme

Dewhurst

et al. 2016

Chemistry A European J

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“…There are relatively few dinuclear compounds with Au-Fe [225][226][227][228] and Au-Ru [229][230][231][232] [230]. The compound IAuOs(m-CH 2 )Cl(NO)(PPh 3 ) 2 193 is the unique dinuclear gold-osmium species characterized by X-ray diffraction and contains metal centers connected at an Au-Os distance of 2.788(1) Å [233].…”

Section: Gold-group 8 Metal Compoundsmentioning

confidence: 99%

Gold–Heterometal Interactions and Bonds

Silvestru

2008

Modern Supramolecular Gold Chemistry

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“…It is noteworthy that isolable and structurally authenticated heterodi- and tri-metallic complexes that feature Ag–Fe bonds without the help of bridging ligands are rather limited and include (Figure ) dinuclear [(p-Tol)Ph 2 P]AgFe(CO) 3 (PMe 3 )(SiPh 2 Me) ( 1 ), and (IPr)AgFe(Cp)(CO) 2 ( 2 ) and the trinuclear [{Fe(CO) 5 } 2 (μ-Ag)][Al{OC(CF 3 ) 3 } 4 ] ( 3 ) and [{Fe(PMe 3 ) 2 (CO) 3 } 2 (μ-Ag)][B(3,5-Cl 2 C 6 H 3 ) 4 ] ( 4 ) . Furthermore, structurally characterized compounds containing the simple, well-known metal carbonyl complex Fe(CO) 5 acting as a ligand are even more rare. , One of these is the trinuclear complex [{Fe(CO) 5 } 2 (μ-Ag)][Al{OC(CF 3 ) 3 } 4 ] ( 3 ) noted above, which involves two Fe(CO) 5 moieties on silver (with an Fe–Ag–Fe core), while the other is an Fe–Ga bonded compound, (CO) 5 FeGaCl 3 .…”

Section: Introductionmentioning

confidence: 99%

“…Structurally characterized heterodi- and tri-metallic complexes that feature unsupported Ag–Fe bonds. − …”

Section: Introductionmentioning

confidence: 99%

Heterobimetallic Silver–Iron Complexes Involving Fe(CO)₅Ligands

et al. 2017

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Iron(0) pentacarbonyl is an organometallic compound with a long history. It undergoes carbonyl displacement chemistry with various donors (L), leading to molecules of the type Fe(CO)(L). The work reported here illustrates that Fe(CO) can also act as a ligand. The reaction between Fe(CO) with the silver salts AgSbF and Ag[B{3,5-(CF)CH}] under appropriate conditions resulted in the formation of [(μ-HO)AgFe(CO)][SbF] and [B{3,5-(CF)CH}]AgFe(CO), respectively, featuring heterobimetallic {Ag-Fe(CO)} fragments. The treatment of [B{3,5-(CF)CH}]AgFe(CO) with 4,4'-dimethyl-2,2'-bipyridine (MeBipy) and Fe(CO) afforded a heterobimetallic [(MeBipy)AgFe(CO)][B{3,5-(CF)CH}] species with a Ag-Fe(CO) bond and a heterotrimetallic [{Fe(CO)}(μ-Ag)][B{3,5-(CF)CH}] with a (CO)Fe-Ag-Fe(CO) core, respectively, illustrating that it is possible to manipulate the coordination sphere at silver while keeping the Ag-Fe bond intact. The chemistry of [B{3,5-(CF)CH}]AgFe(CO) with EtO and PMes (Mes = 2,4,6-trimethylphenyl) has also been investigated, which led to [(EtO)Ag][B{3,5-(CF)CH}] and [(MesP)Ag][B{3,5-(CF)CH}] with the displacement of the Fe(CO) ligand. X-ray structural and spectroscopic data of new molecules as well as results of computational analyses are presented. The Fe-Ag bond distances of these metal-only Lewis pairs range from 2.5833(4) to 2.6219(5) Å. These Ag-Fe bonds are of primarily an ionic/electrostatic nature with a modest amount of charge transfer between Ag and Fe(CO). The ν̅(CO) bands of the molecules with Ag-Fe(CO) bonds show a notable blue shift relative to those observed for free Fe(CO), indicating a significant reduction in Fe→CO back-bonding upon its coordination to silver(I).

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Übergangsmetall-silyl-komplexe

Cited by 36 publications

References 10 publications

Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation

Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation

Gold–Heterometal Interactions and Bonds

Heterobimetallic Silver–Iron Complexes Involving Fe(CO)₅Ligands

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Übergangsmetall-silyl-komplexe

Cited by 36 publications

References 10 publications

Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation

Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation

Gold–Heterometal Interactions and Bonds

Heterobimetallic Silver–Iron Complexes Involving Fe(CO)5Ligands

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Heterobimetallic Silver–Iron Complexes Involving Fe(CO)₅Ligands