Organo-Transition Metal Compounds Containing Perfluorinated Ligands

Hughes, Russell P.

doi:10.1016/s0065-3055(08)60511-0

Cited by 108 publications

(34 citation statements)

References 169 publications

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“…Treatment of the resulting residue with iPrOH (3 mL) at 0 8C rendered a white solid, which was filtered, washed with nhexane (3 3 mL), dried in vacuo, and identified as 7 (0.15 g, 0.17 mmol, 77 % yield). 1 Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of 7 (5 mg) in CHCl 3 (2 mL) at room temperature. X-ray structure determinations: Crystal data and other details of the structure analyses are presented in Table 3.…”

Section: Methodsmentioning

confidence: 99%

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Highly Trifluoromethylated Platinum Compounds

Martínez-Salvador

Forniés

Martín

et al. 2011

Chemistry A European J

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The homoleptic, square‐planar organoplatinum(II) compound [NBu4]2[Pt(CF3)4] (1) undergoes oxidative addition of CF3I under mild conditions to give rise to the octahedral organoplatinum(IV) complex [NBu4]2[Pt(CF3)5I] (2). This highly trifluoromethylated species reacts with Ag+ salts of weakly coordinating anions in Me2CO under a wet‐air stream to afford the aquo derivative [NBu4][Pt(CF3)5(OH2)] (4) in around 75 % yield. When the reaction of 2 with the same Ag+ salts is carried out in MeCN, the solvento compound [NBu4][Pt(CF3)5(NCMe)] (5) is obtained in around 80 % yield. The aquo ligand in 4 as well as the MeCN ligand in 5 are labile and can be cleanly replaced by neutral and anionic ligands to furnish a series of pentakis(trifluoromethyl)platinate(IV) compounds with formulae [NBu4][Pt(CF3)5(L)] (L=CO (6), pyridine (py; 7), tetrahydrothiophene (tht; 8)) and [NBu4]2[Pt(CF3)5X] (X=Cl (9), Br (10)). The unusual carbonyl–platinum(IV) derivative [NBu4][Pt(CF3)5(CO)] (6) is thermally stable and has a νCO of 2194 cm−1. The crystal structures of 2⋅CH2Cl2, 5, [PPh4][Pt(CF3)5(CO)] (6′), and 7 have been established by X‐ray diffraction methods. Compound 2 has shown itself to be a convenient entry to the chemistry of highly trifluoromethylated platinum compounds. To the best of our knowledge, compounds 2 and 4–10 are the organoelement compounds with the highest CF3 content to have been isolated and adequately characterized to date.

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Section: Methodsmentioning

confidence: 99%

“…In our opinion, it is not advisable to use intermolecular criteria (such as van der Waals radii) to decide on the existence of intramolecular phenomena. In view of the long PtÀCO bond and the small 1 …”

Section: (Co)]mentioning

confidence: 99%

Highly Trifluoromethylated Platinum Compounds

Martínez-Salvador

Forniés

Martín

et al. 2011

Chemistry A European J

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“…Factors affecting the stability of transition-metal bonds to carbon are of continued interest and fluorocarbon transition-metal derivatives are especially interesting [115][116][117] because of their generally enhanced stability, relative to hydrocarbon analogues. Factors that could enhance stability include the electronegativity of fluorocarbon groups, which will tend to increase the energy gap between s and s Ã orbitals in the bonds to transition metals.…”

Section: Transition Metalsmentioning

confidence: 99%

“…For a wider discussion of fluorocarbon-transition-metal derivatives, and aspects such as their bonding, the reader is referred to other sources [115][116][117].…”

Section: Transition Metalsmentioning

confidence: 99%

Organometallic Compounds

2004

Fluorine in Organic Chemistry

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“…19,20 Particularly interesting synthetic targets are the fluorinated analogues of sandwich compounds such as ferrocene. 19,20 Particularly interesting synthetic targets are the fluorinated analogues of sandwich compounds such as ferrocene.…”

Section: Introductionmentioning

confidence: 99%

Triple decker sandwiches and related compounds of the first row transition metals with cyclopentadienyl and hexafluorobenzene rings: remarkable effects of fluorine substitution

Gong

Luo

Feng

et al. 2015

Phys. Chem. Chem. Phys.

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The complete series of Cp2M2(μ-C6F6) (M = Ti, V, Cr, Mn, Fe, Co, Ni) structures have been examined theoretically for comparison with their unsubstituted Cp2M2(μ-C6H6) analogues. The singlet triple decker sandwich titanium complex Cp2Ti2(η(6),η(6)-C6F6) with a closed shell electronic structure and a non-planar C6F6 ring is preferred energetically by a wide margin (>20 kcal mol(-1)) over other isomers and spin states. This is in contrast to the hydrogen analogue for which related triplet spin state structures are clearly preferred. A similar low-energy triple-decker sandwich Cp2V2(η(6),η(6)-C6F6) structure is found for vanadium but with a quintet spin state. The later transition metals from Cr to Ni energetically prefer the so-called "rice-ball" cis-Cp2M2(μ-C6F6) structures with varying hapticities of metal-ring bonding, a range of formal orders of metal-metal bonding, and varying spin states depending on the metal atom. Thus the lowest energy Cp2Cr2(μ-C6F6) structures are triplet and quintet structures with pentahapto-trihapto η(5),η(3)-μ-C6F6 rings and formal Cr=Cr double bonds. This contrasts with the structure of Cp2Cr2(μ-C6H6) having a bis(tetrahapto) η(4),η(4)-C6H6 ring and a formal Cr-Cr quadruple bond. The lowest energy Cp2Mn2(μ-C6F6) structures are trans and cis quintet spin state structures. This contrasts with Cp2Mn2(μ-C6H6) for which a closed-shell singlet triple decker sandwich structure is preferred. The lowest energy Cp2Fe2(μ-C6F6) structure is a triplet cis structure with a tetrahapto-dihapto η(4),η(2)-μ-C6F6 ring and a formal Fe-Fe single bond. The lowest energy Cp2Co2(μ-C6F6) structures are singlet spin state structures with formal M-M single bonds and either bridging bis(trihapto) η(3),η(3)-C6F6 or tetrahapto-dihapto η(4),η(2)-C6F6 rings. For Cp2Ni2(μ-C6F6) low energy singlet cis and trans structures are both found. The singlet cis-Cp2Ni2(μ-C6F6) structure has a Ni-Ni single bond of length ∼2.5 Å and a bridging bis(dihapto) η(2),η(2)-C6F6 ligand with an uncomplexed C=C double bond. The singlet trans-Cp2Ni2(μ-C6F6) structure has a bis(trihapto) η(3),η(3)-C6F6 ligand.

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Organo-Transition Metal Compounds Containing Perfluorinated Ligands

Cited by 108 publications

References 169 publications

Highly Trifluoromethylated Platinum Compounds

Highly Trifluoromethylated Platinum Compounds

Organometallic Compounds

Triple decker sandwiches and related compounds of the first row transition metals with cyclopentadienyl and hexafluorobenzene rings: remarkable effects of fluorine substitution

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