Reaction of Nonmetal Fluorides with Some Platinum Metal Complexes

Cockman, R. W.; Ebsworth, E. A. V.; Holloway, John H.; Murdoch, H. D.; Robertson, Neil; Watson, Paul G.

doi:10.1021/bk-1994-0555.ch020

Cited by 18 publications

(32 citation statements)

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“…The coupling constants are entirely consistent with previously reported 2 J FF interactions on iridium(III) {IrF 3 (CO)(PEt 3 ) 2 2 J FF = 96 Hz; IrClF 2 (CO)(PEt 3 ) 2 2 J FF = 115 Hz; IrBrF 2 (CO)(PEt 3 ) 2 2 J FF = 130 Hz}. 17 19 F data is diagnostic of an F-trans-F stereochemistry (Table 3; Scheme 1). Each of these iridium(III)-NHC fluoride complexes decompose inconsistently in solution in a few hours, always with loss of the metal-bound fluoride resonances and generation of HF, which precluded all our attempts to grow crystals suitable for structural characterisation.…”

Section: Results and Discussion (A) Ligand Displacement Reactions Wit...supporting

confidence: 90%

“…In light of the failure to use ligand metathesis for the synthesis of iridium(III)-fluoride-NHC complexes, we turned our attention to our second, oxidative addition, route (Scheme 1). We, 8 and others, 17 have shown that XeF 2 readily oxidises a variety of neutral and cationic iridium(I) phosphine complexes containing carbonyl, halide and/or COD (1,5-cyclooctadiene) to form iridium(III) difluoride complexes. Since, monosubstituted neutral and cationic complexes of iridium(I), particularly those with COD or CO ligands, are amongst the most extensively investigated metal carbene derivatives, 18 these provided an ideal series for our investigation.…”

Section: Results and Discussion (A) Ligand Displacement Reactions Wit...mentioning

confidence: 90%

“…Each of these iridium(III)-NHC fluoride complexes decompose inconsistently in solution in a few hours, always with loss of the metal-bound fluoride resonances and generation of HF, which precluded all our attempts to grow crystals suitable for structural characterisation. However, crystallographic studies on one of the products, a C-H activated IMes complex, 17) in dichloromethane, revealed insight into the decomposition process (Fig. 6).…”

Section: Results and Discussion (A) Ligand Displacement Reactions Wit...mentioning

confidence: 99%

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Stabilisation of iridium(iii) fluoride complexes with NHCs

et al. 2010

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The first neutral, [IrClF(2)(NHC)(COD)] and [IrClF(2)(CO)(2)(NHC)] (NHC = IMes, IPr), and cationic, [IrF(2)py(IMes)(COD)][BF(4)] and [IrF(2)L(CO)(2)(NHC)][BF(4)] (NHC = IMes, L = PPh(2)Et, PPh(2)CCPh, py; NHC = IPr, L = py), NHC iridium(III) fluoride complexes, have been synthesised by the xenon difluoride oxidation of iridium(I) substrates. The stereochemistries of these iridium(III) complexes have been confirmed by multinuclear NMR spectroscopy in solution and no examples of fluoride-trans-NHC arrangements were observed. Throughout, CO was found to be a better co-ligand for the stabilisation of the iridium(III) fluoride complexes than COD. Attempts to generate neutral trifluoroiridium(III) complexes, [IrF(3)(CO)(NHC)], via the ligand substitution reaction of [IrF(3)(CO)(3)] with the free NHCs were unsuccessful.

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Section: Results and Discussion (A) Ligand Displacement Reactions Wit...supporting

confidence: 90%

Section: Results and Discussion (A) Ligand Displacement Reactions Wit...mentioning

confidence: 90%

Section: Results and Discussion (A) Ligand Displacement Reactions Wit...mentioning

confidence: 99%

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Stabilisation of iridium(iii) fluoride complexes with NHCs

et al. 2010

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“…For the all-trans isomers, the 19 F NMR resonances occur at substantially lower frequencies and the 2 J PF coupling constants are larger than those for the cis-difluoride isomers, as expected for the F-trans-F and F-cis-F arrangements. 13,[21][22][23][24] In the oxidations of the a-diimine complexes, the corresponding iridium(III) difluoride cations are formed as the single F-trans-F isomers, trans-,cis- 2), for which the shifts in d F to low frequency, in comparison to those for the related COD-complexes, mirror those for the related pairs of monodentate phosphine complexes.…”

Section: Methodsmentioning

confidence: 99%

“…Found: C, 52. The other iridium difluorocations (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22) were prepared similarly in quantitative yields.…”

Section: Experimental General Remarksmentioning

confidence: 99%

Synthesis and characterisation of some iridium-carbonyl-fluoride complexes. Crystal structures of [IrF(CO){P(C6H4-2-CH3)3}2] and [IrF2(COD)py2][BF4]

2010

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Two routes to iridium(III) fluorocomplexes are described. The direct reaction of tetrairidium dodecacarbonyl with elemental fluorine in aHF offers a clean, convenient, large scale route to [IrF(3)(CO)(3)]; addition of phosphines to [IrF(3)(CO)(3)] in THF affords mer-[IrF(3)(CO)L(2)] or [IrF(CO)L(2)]. Alternatively, cationic [IrF(2)(COD)L(2)](+) and [IrF(2)(CO)(2)L(2)](+) (L = phosphine, pyridine; L(2) = alpha-diimine) are accessible via the oxidation of the iridium(I) precursors with xenon difluoride.

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Reactivity of Binary and Ternary Sulfur Halides towards Transition‐Metal Compounds

Dirican

Pfister

Wozniak

et al. 2020

Chemistry A European J

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Binary sulfur fluorides exhibit an interesting reactivity towards transition metal complexes. They open up routes for the generation of sulfur‐containing building blocks. Often ligands with particular properties can be constructed. This includes their ability to transfer sulfur atoms or polysulfide units as well as fluorination reactions. This Minireview provides an insight into the reactivity of the binary and ternary sulfur halides S2Cl2, SCl2, SF4, SF6 and SF5Cl towards transition‐metal compounds.

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Reaction of Nonmetal Fluorides with Some Platinum Metal Complexes

Cited by 18 publications

References 0 publications

Stabilisation of iridium(iii) fluoride complexes with NHCs

Stabilisation of iridium(iii) fluoride complexes with NHCs

Synthesis and characterisation of some iridium-carbonyl-fluoride complexes. Crystal structures of [IrF(CO){P(C6H4-2-CH3)3}2] and [IrF2(COD)py2][BF4]

Reactivity of Binary and Ternary Sulfur Halides towards Transition‐Metal Compounds

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