Bis(Phosphine) Derivatives of Iron Pentacarbonyl and Tetracarbonyl (Tri‐
            <i>tert</i>
            ‐Butylphosphine)Iron(O)

Therien, Michael J.; Trogler, William C.; Silva, Rosalice; Darensbourg, Marcetta Y.

doi:10.1002/9780470132593.ch45

Cited by 15 publications

(4 citation statements)

References 10 publications

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“…However, when a solution of 8 was heated to 68 °C, compound 8 decomposed with formation of the mononuclear iron compound 11 in 31% yield and, presumably, Pd metal. Compound 11 was identified by its IR spectrum and the unit cell dimensions of its crystalline form . Compound 11 was previously synthesized from Fe(CO) 5 and PBu t 3 but requires UV irradiation for 8 h …”

Section: Resultsmentioning

confidence: 99%

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Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe₂(CO)₉[M(PBu^t₃)]₂(M = Pd or Pt) and Fe₂(CO)₈[Pt(PBu^t₃)]₂(μ-H)₂

2006

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The reaction of Fe2(CO)9 with Pd(PBu(t)3)2 and Pt(PBu(t)3)2 yielded the Fe-Pd and Fe-Pt cluster complexes Fe2(CO)9[M(PBu(t)3)]2, M = Pd (8) or Pt (9). The structures of 8 and 9 are analogous and consist of nearly planar butterfly clusters of two palladium/platinum atoms in the wing-tip positions and two mutually bonded iron atoms, Fe-Fe = 2.9582(11) A in 8 and 2.9100 (9) A in 9. Compound 8 decomposes to form the mononuclear iron compound Fe(CO)4(PBu(t)3) (11) when heated at 68 degrees C. The reaction of Pt(PBu(t)3)2 with Fe2(CO)9 in the presence of hydrogen at 127 degrees C yielded the dihydrido complex Fe2(CO)8[Pt(PBu(t)3)]2(mu-H)2 (10). Compound 10 contains a closed Fe2Pt2 tetrahedral cluster with hydrido ligands bridging two of the Fe-Pt bonds. Compounds 8, 9, and 10 were structurally characterized crystallographically.

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Section: Resultsmentioning

confidence: 99%

“…Compound 11 was identified by its IR spectrum and the unit cell dimensions of its crystalline form . Compound 11 was previously synthesized from Fe(CO) 5 and PBu t 3 but requires UV irradiation for 8 h …”

Section: Resultsmentioning

confidence: 99%

Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe₂(CO)₉[M(PBu^t₃)]₂(M = Pd or Pt) and Fe₂(CO)₈[Pt(PBu^t₃)]₂(μ-H)₂

2006

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“…The simultaneous formation of [Fe(CO) 3 (PMe 3 ) 2 ] was confirmed by 1 H and 31 P{ 1 H} NMR spectroscopy. 40,41 On the basis of the previous work using [Fe 2 (μ-PyBPT)(CO) 5 ], we expected that the reaction was initiated by the substitution of PMe 3 for CO in the Fe(CO) 3 unit, followed by the further reaction of PMe 3 , involving heterolytic Fe−Fe bond cleavage. 39 Because the first step involves the dissociation of the π-coordinated moiety, the stronger π-binding could reduce the reaction rate.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Iron Carbonyl Complexes Containing N,C,S-Tridentate Ligands with Quinoline, Vinyl, and Benzenethiolate Units

et al. 2020

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Iron(III) carbonyl complexes of N,C,S-tridentate ligands containing quinoline-N, vinyl-C, and benzenethiolate-S donors were synthesized by three steps from quinolyl-substituted benzothiophenes via C–S bond cleavage, and their photoreactivity was investigated. The starting complexes [Fe2(μ-L)(CO)5] (L = qvbt and qvbt-OMe) were synthesized by the photoreactions of the ligand precursors with [Fe(CO)5], where qvbt and qvbt-OMe are a doubly deprotonated form of 2-[2-(quinolin-8-yl)vinyl]benzenethiol and its methoxy derivative, respectively. The methoxy group is bound to the vinyl moiety of the ligand, which is the β-position to Fe in the C,S-chelate. The N,C,S-pincer iron(II) carbonyl complexes trans-[Fe(L)(CO)(PMe3)2] were obtained by treatment of [Fe2(μ-L)(CO)5] with PMe3. One-electron oxidation of the iron(II) complexes afforded the N,C,S-pincer iron(III) carbonyl complexes trans-[Fe(L)(CO)(PMe3)2]PF6. The iron(III) carbonyl complex of qvbt was adequately stable in both the solid and solution state, whereas the qvbt-OMe complex underwent thermal decomposition in solution. The instability is related to the steric demand of the methoxy group in the coordinated ligand. Both iron(III) complexes showed the CO-releasing properties induced by visible light in dichloromethane, which is enhanced by the methoxy group on the vinyl moiety.

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“…The Fe(CO) 5 is a molecule with a more than 125-year history . It most typically undergoes carbonyl displacement chemistry with a variety of donors (L), leading to molecules of the type Fe(CO) x (L) 5– x . ,,− Compounds such as [(μ-H 2 O)AgFe(CO) 5 ] 2 [SbF 6 ] 2 ( 5 ), [B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ]AgFe(CO) 5 ( 6 ), [(Me 2 Bipy)AgFe(CO) 5 ][B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ] ( 7 ), and [{Fe(CO) 5 } 2 (μ-Ag)][B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ] ( 8 ) demonstrate a different facet of Fe(CO) 5 in which it acts as a Lewis base. X-ray crystal structures show that these molecules feature heterometallic Ag–Fe(CO) 5 bonds.…”

Section: Discussionmentioning

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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Bis(Phosphine) Derivatives of Iron Pentacarbonyl and Tetracarbonyl (Tri‐ tert ‐Butylphosphine)Iron(O)

Cited by 15 publications

References 10 publications

Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe₂(CO)₉[M(PBu^t₃)]₂(M = Pd or Pt) and Fe₂(CO)₈[Pt(PBu^t₃)]₂(μ-H)₂

Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe₂(CO)₉[M(PBu^t₃)]₂(M = Pd or Pt) and Fe₂(CO)₈[Pt(PBu^t₃)]₂(μ-H)₂

Iron Carbonyl Complexes Containing N,C,S-Tridentate Ligands with Quinoline, Vinyl, and Benzenethiolate Units

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

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Bis(Phosphine) Derivatives of Iron Pentacarbonyl and Tetracarbonyl (Tri‐ tert ‐Butylphosphine)Iron(O)

Cited by 15 publications

References 10 publications

Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe2(CO)9[M(PBut3)]2(M = Pd or Pt) and Fe2(CO)8[Pt(PBut3)]2(μ-H)2

Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe2(CO)9[M(PBut3)]2(M = Pd or Pt) and Fe2(CO)8[Pt(PBut3)]2(μ-H)2

Iron Carbonyl Complexes Containing N,C,S-Tridentate Ligands with Quinoline, Vinyl, and Benzenethiolate Units

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

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Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe₂(CO)₉[M(PBu^t₃)]₂(M = Pd or Pt) and Fe₂(CO)₈[Pt(PBu^t₃)]₂(μ-H)₂

Bimetallic Clusters of Iron with Palladium and Platinum. Synthesis and Structures of Fe₂(CO)₉[M(PBu^t₃)]₂(M = Pd or Pt) and Fe₂(CO)₈[Pt(PBu^t₃)]₂(μ-H)₂

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