C-C versus C-H activation and versus agostic C-C interaction controlled by electron density at the metal center

Based on the PCN ligand 2, a remarkable degree of control over C-C versus C-H bond activation and versus formation of an agostic C-C complex was demonstrated by choice of cationic [Rh(CO)(n)(C(2)H(4))(2-n)] (n=0, 1, 2) precursors. Whereas reaction of 2 with [Rh(C(2)H(4))(2)(solv)(n)]BF(4) results in exclusive C-C bond activation to yield product 5, reaction with the dicarbonyl precursor [Rh(CO)(2)(solv)(n)]BF(4) leads to formation of the C-H activated complex 9. The latter process is promoted by intramolecular deprotonation of the C-H bond by the hemilabile amine arm of the PCN ligand. The mixed monocarbonyl monoethylene Rh species [Rh(CO)(C(2)H(4))]BF(4) reacts with the PCN ligand 2 to give an agostic complex 7. The C-C activated complex 5 is easily converted to the C-H activated one (9) by reaction with CO; the reaction proceeds by a unique sequence of 1,2-metal-to-carbon methyl shift, agostic interaction, and C-H activation processes. Similarly, the C-C agostic complex 7 is converted to the same C-H activated product 9 by treatment with CO.     

BINAP: rhodium–diolefin complexes in asymmetric hydrogenation

The complexes [Rh((S)-BINAP)(COD)]BF₄ 1, [Rh((S)-BINAP)(NBD)]BF₄ 2, [Rh((R)-BINAP)(COD)]OTf 3, [Rh((R)-BINAP)(NBD)]OTf 4, and [Rh((R)-BINAP)(COD)]BArF 5 were synthesized, and 1–4 were analyzed by single crystal X-ray crystallography. The transformation of these precatalysts into hydrogenation-active species was investigated as well as the hydrogenation of prochiral olefins. In particular, this series of transformations was investigated with regard to solvent and counterions.     

Rhodium nitrosyl catalysts for CO2 hydrogenation to formic acid under mild conditions

A new synthetic protocol for catalysing CO₂ hydrogenation to formic acid under mild conditions is reported, and the CO₂ hydrogenation is efficiently achieved by dcpe‐rhodium‐nitrosyl catalyst precursors, Rh(NO)(dcpe) (1) (dcpe = 1,2‐dicyclohexylphosphinoethane) and Rh(III)(NO)(dcpe)Cl₂ (2). The catalytic activity of 1 is noteworthy for being able to proceed in the absence of protic conditions. Compound 2 is characterized by NMR, IR and X‐ray crystallography. In particular, 2 is observed to bear a bent NO ligand with a Rh–N–O angle of 115.7(3)°, representing one of the smallest M–N–O angles known. Copyright © 2012 John Wiley & Sons, Ltd.     

Interplay between solvent and counteranion stabilization of highly unsaturated rhodium(III) complexes: facile unsaturation-induced dearomatization

Abstraction of the chloride ligand from the PCN-based chloromethylrhodium complex 2 by AgX (X=BF(4)(-), CF(3)SO(3)(-)) or a direct C-C cleavage reaction of the PCN ligand 1 with [(coe)(2)Rh(solv)(n)](+)X(-) (coe=cyclooctene) lead to the formation of the coordinatively unsaturated rhodium(III) complexes 3. Compound 3 a (X=BF(4)(-)) exhibits a unique medium effect; the metal center is stabilized by reversible coordination of the bulky counteranion or solvent as a function of temperature. Reaction of [(PCN)Rh(CH(3))(Cl)] with AgBAr(f) in diethyl ether leads to an apparent rhodium(III) 14-electron complex 4, which is stabilized by reversible, weak coordination of a solvent molecule. This complex coordinates donors as weak as diethyl ether and dichloromethane. Upon substitution of the BF(4)(-) ion in [(PCN)Rh(CH(3))]BF(4) by the noncoordinating BAr(f)(-) ion in a noncoordinating medium, the resulting highly unsaturated intermediate undergoes a 1,2-metal-to-carbon methyl shift, followed by beta-hydrogen elimination, leading to the Rh-stabilized methylene arenium complex 5. This process represents a unique mild, dearomatization of the aromatic system induced by unsaturation.     

Multi-site reactivity: reduction of six equivalents of nitrite to give an Fe6(NO)6 cluster with a dramatically expanded octahedral core

Reaction of NO(2)(-) with the octahedral cluster ((H)L)(2)Fe(6) in the presence of a proton source affords the hexanitrosyl cluster ((H)L)(2)Fe(6)(NO)(6). This species forms via a proton-induced reduction of six nitrite molecules per cluster, utilizing each site available on the polynuclear core. Formation of the hexanitrosyl cluster is accompanied by a near 2-fold expansion of the ((H)L)(2)Fe(6) core volume, where intracore Fe-Fe interactions are overcome by strong π-bonding between Fe centers and NO ligands. A core volume of this magnitude is rare in octahedral metal clusters not supported by interstitial atoms. Moreover, the structural flexibility afforded by the ((H)L)(2)Fe(6) platform highlights the potential for other reaction chemistry involving species with metal-ligand multiple bonds. Carrying out the reaction of the cluster [((H)L)(2)Fe(6)(NCMe)(6)](4+) with nitrite in the absence of a proton source serves to forestall the nitrite reduction and enables clean isolation of the intermediate hexanitro cluster [((H)L)(2)Fe(6)(NO(2))(6)](2-).     

Kinetic Study of the Oxidative Addition Reaction between Methyl Iodide and [Rh(imino-β-diketonato)(CO)(PPh)3] Complexes,Utilizing UV–Vis,IR Spectrophotometry,NMR Spectroscopy and DFT Calculations

The oxidative addition of methyl iodide to [Rh(β-diketonato)(CO)(PPh)₃] complexes, as modal catalysts of the first step during the Monsanto process, are well-studied. The β-diketonato ligand is a bidentate (BID) ligand that bonds, through two O donor atoms (O,O-BID ligand), to rhodium. Imino-β-diketones are similar to β-diketones, though the donor atoms are N and O, referred to as an N,O-BID ligand. In this study, the oxidative addition of methyl iodide to [Rh(imino-β-diketonato)(CO)(PPh)₃] complexes, as observed on UV–Vis spectrophotometry, IR spectrophotometry and NMR spectrometry, are presented. Experimentally, one isomer of [Rh(CH₃COCHCNPhCH₃)(CO)(PPh₃)] and two isomers of [Rh(CH₃COCHCNHCH₃)(CO)(PPh₃)] are observed—in agreement with density functional theory (DFT) calculations. Experimentally the [Rh(CH₃COCHCNPhCH₃)(CO)(PPh₃)] + CH₃I reaction proceeds through one reaction step, with a rhodium(III)-alkyl as the final reaction product. However, the [Rh(CH₃COCHCNHCH₃)(CO)(PPh₃)] + CH₃I reaction proceeds through two reaction steps, with a rhodium(III)-acyl as the final reaction product. DFT calculations of all the possible reaction products and transition states agree with experimental findings. Due to the smaller electronegativity of N, compared to O, the oxidative addition reaction rate of CH₃I to the two [Rh(imino-β-diketonato)(CO)(PPh)₃] complexes of this study was 7–11 times faster than the oxidative addition reaction rate of CH₃I to [Rh(CH₃COCHCOCH₃)(CO)(PPh₃)].     

Synthesis and characterization of two acetato-bridged dinuclear copper(II) complexes with 4-bromo-2-((4 or 6-methylpyridin-2-ylimino)methyl)phenol as ligand

The synthesis and characterization of two new acetato-bridged dinuclear copper(II) complexes are described. Both compounds have the general formula [Cu(L)(µ-O₂C–CH₃)]₂, in which L = 4-bromo-2-((4-methylpyridin-2-ylimino)methyl)phenol or 4-bromo-2-((6-methylpyridin-2-ylimino)methyl)phenol. The title compounds consist of dinuclear units with bridging acetato groups and a ligand linked to each copper via the phenol oxygen and nitrogen. Both compounds were synthesized in a one-step reaction and characterized by elemental analysis, Fourier transform infrared (FTIR), electron spin resonance (ESR), and electronic spectra and by room temperature magnetic moments. The compounds exhibit antiferromagnetic interactions at room temperature. UV-Vis spectra show four absorptions attributed to d–d transitions of copper, ligand → metal charge transfer and π → π* or n → π* transitions of ligand. The FTIR spectra indicate a Cu₂O₄C₂ ring vibration. Both complexes show room temperature magnetic moments of about 1.6 B.M. per copper. The X-band ESR studies indicate a weak half-field band, characteristic of the Cu(II)–Cu(II) dimer, observed at 1552 and 1558 G for the complexes, strongly suggesting that the hyperfine structure arises from a spin triplet species. The spectra of frozen samples in DMSO or DMF at liquid nitrogen temperature show a typical Δm = 1 transition.     

Iodomethane oxidative addition and CO migratory insertion in monocarbonylphosphine complexes of the type [Rh((C6H5)COCHCO((CH2)nCH3))(CO)(PPh3)]: Steric and electronic effects

The chemical kinetics, studied by UV/Vis, IR and NMR, of the oxidative addition of iodomethane to [Rh((C₆H₅)COCHCOR)(CO)(PPh₃)], with R = (CH₂)_nCH₃, n = 1-3, consists of three consecutive reaction steps that involves isomers of two distinctly different classes of Rh^III-alkyl and two distinctly different classes of Rh^III-acyl species. Kinetic studies on the first oxidative addition step of [Rh((C₆H₅)COCHCOR)(CO)(PPh₃)] + CH₃I to form [Rh((C₆H₅)COCHCOR)(CH₃)(CO)(PPh₃)(I)] revealed a second order oxidative addition rate constant approximately 500-600 times faster than that observed for the Monsanto catalyst [Rh(CO)₂I₂]⁻. The reaction rate of the first oxidative addition step in chloroform was not influenced by the increasing alkyl chain length of the R group on the β-diketonato ligand: k₁ = 0.0333 ([Rh((C₆H₅)COCHCO(CH₂CH₃))(CO)(PPh₃)]), 0.0437 ([Rh((C₆H₅)COCHCO(CH₂CH₂CH₃))(CO)(PPh₃)]) and 0.0354 dm³ mol⁻¹ s⁻¹ ([Rh((C₆H₅)COCHCO(CH₂CH₂CH₂CH₃))(CO)(PPh₃)]). The pK_a^′ and keto-enol equilibrium constant, K_c, of the β-diketones (C₆H₅)COCH₂COR, along with apparent group electronegativities, χ_R of the R group of the β-diketones (C₆H₅)COCH₂COR, give a measurement of the electron donating character of the coordinating β-diketonato ligand: (R, pK_a^′, K_c, χ_R) = (CH₃, 8.70, 12.1, 2.34), (CH₂CH₃, 9.33, 8.2, 2.31), (CH₂CH₂CH₃, 9.23, 11.5, 2.41) and (CH₂CH₂CH₂CH₃, 9.33, 11.6, 2.22).     

Highly enantioselective catalytic hydrogenation of a 5-amino-3,5-dioxopentanoic ester

The highly enantioselective hydrogenation of methyl 4-tert-butylcarbamoyl-3-oxo-butyrate to the corresponding secondary alcohol, representing an interesting chiral building block, for example, for the synthesis of statins, has been investigated in the presence of homogeneous chiral Rh(I) and Ru(II) complexes bearing phosphine ligands. The highest enantioselectivity (up to 96%) was achieved with a [Ru((R)-BINAP)(p-cymene)Cl]Cl complex (sub./cat. ratio 100:1, 5 bar H₂, rt, MeOH).     

Novel binuclear rhodium complexes containing ketonic carbonyl and acetylene ligands

The reaction of trans-[RhCl(CO)(DPM)]₂ (DPM = Ph₂PCH₂PPh₂) with dimethylacetylenedicarboxylate (DMA) and hexafluoro-2-butyne (HFB) yield the novel species [Rh₂Cl₂(μ-CO)(μ-Acet)(DPM)₂] (Acet = DMA, HFB). The X-ray structure determination of the DMA derivative indicates that the complex has the acetylene molecule coordinated as a cis-dimetallated olefin and also contains a ketonic carbonyl ligand. The long Rh?Rh separation (3.3542(9) Å) suggests no metal—metal bond and the RhC(O)Rh angle (116.0(4)°) suggest sp² hybridization of the carbonyl carbon atom. Similarly the geometry at the acetylene ligand and the CC distance of the coordinated acetylene moiety (1.32(1) Å) are consistent with the dimetallated olefinic formulation. This represents the first reported characterization of a ketonic carbonyl complex outside the Ni triad. These novel complexes have also been formed by the direct insertion of the acetylene molecules into the formal RhRh bond in [Rh₂Cl₂(μ-CO)(DPM)₂].     

New nitrosyl(perfluorocarboxylato) complexes of the platinum metals

Perfluorocarboxylic acids (R_FCOOH) (R_F = CF₃,C₂F₅ and (for Rh) C₆F₅) react with the species [M(NO)₂(PPh₃)₂] (M = Ru, Os) and [M′(NO)(PPh₃)₃] (M′ = Rh, Ir) to yield new nitrosyl complexes [Ru(OCOR_F)₃(NO)(PPh₃)₂], [OsH(OCOR_F)₂(NO)(PPh₃)₂], [Os(OCOR_F)(NO)₂(PPh₃)₂][OCOR_F], [Ir(OCOR_F)(NO)(PPh₃)₂][OCOR_F] and [Rh(OCOR_F)₂(NO)(PPh₃)₂].     

Oxidative addition of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)]: an experimental and computational study

The reaction rate of the oxidative addition and CO insertion steps of methyl iodide with [Rh(PhCOCHCOPh)(CO)(P(OCH₂)₃CCH₃)] are presented. Large negative experimental values for the activation entropy and results from a density functional theory computational chemistry study indicated trans addition of the CH3I to [Rh(PhCOCHCOPh)(CO)(P(OCH₂)₃CCH₃)]. A study of the molecular orbitals gives insight into the flow of electrons during the oxidative addition reaction. CO insertion leads to a square pyramidal [Rh(PhCOCHCOPh)(P(OCH₂)₃CCH₃)(COCH₃)(I)] acyl product with the COCH3 moiety in the apical position. The strong electron donation of the P(OCH₂)₃CCH₃ ligand accelerates the oxidation addition step of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH₂)₃CCH₃)] by ca. 265 times faster (at 35°C) than that of the Monsanto catalyst, but inhibits the CO insertion step.     

Economizing on Precious Metals in Three‐Way Catalysts: Thermally Stable and Highly Active Single‐Atom Rhodium on Ceria for NO Abatement under Dry and Industrially Relevant Conditions**

We show for the first time that atomically dispersed Rh cations on ceria, prepared by a high‐temperature atom‐trapping synthesis, are the active species for the (CO+NO) reaction. This provides a direct link with the organometallic homogeneous Rh^I complexes capable of catalyzing the dry (CO+NO) reaction. The thermally stable Rh cations in 0.1 wt % Rh₁/CeO₂ achieve full NO conversion with a turn‐over‐frequency (TOF) of around 330 h^?1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N₂ with N₂O being the minor product. The presence of water promotes low‐temperature activity of 0.1 wt % Rh₁/CeO₂. In the wet stream, ammonia and nitrogen are the main products above 120 °C. The uniformity of Rh ions on the support, allows us to detect the intermediates of (CO+NO) reaction via IR measurements on Rh cations on zeolite and ceria. We also show that NH₃ formation correlates with the water gas shift (WGS) activity of the material and detect the formation of Rh hydride species spectroscopically.     

Carbonyl nitrosyl derivatives of rhodium and their reaction with silver nitrate

Summary Solid sodium nitrite and moderately concentrated hydrochloric acid react with [ittrans]-Rh(CO)XL₂ (X = Cl, Br, I and L = PPh₃, AsPh₃) dissolved in either DMF or CHCl₃ to yield carbonyl nitrosyl derivatives of the type Rh(CO)(NO)L₂XCI. These brown crystalline products are monomeric nonelectrolytes. Their absorption bands atca. 1630 cm^–1 andca. 2 100 cm^–1 indicate the presence of nitrosyl as well as carbonyl groups. Silver nitrate reacts with the Rh(CO)(NO)L₂XCI complexes to yield pentacoordinate species having the general composition Rh(NO)(NO₃)₂L2.     

Batch and Continuous Flow Hydrogenation of Liquid and Gaseous Alkenes Catalyzed by a Silica‐grafted Iridium(III) Hydride

The silica‐grafted hydride complex [IrH(SBA‐15)(PCP)] ( 2a ; PCP = 1,3‐bis((di‐tert‐butylphosphino)methyl)benzene) hydrogenates alkenes under ambient condition without prior activation. Compared to its POCOP analogue (POCOP = 1,3‐bis((di‐tert‐butylphosphino)oxy)benzene), the activity of catalyst 2a is significantly improved with liquid substrates and exceptionally boosted with ethene and propene. Under gas flow conditions, catalyst 2a hydrogenates ethene with a remarkable turnover frequency of 0.95 s^?1. A stability test indicates that the conversion is constant for at least 1 week.     

Reactivity and stability of platinum(II) formyl complexes based on PCP-type ligands. The significance of sterics

The synthesis and characterization of several Pt(ii) complexes, including formyl complexes, based on the PCP-type pincer ligands C(6)H(4)[CH(2)P(iPr)(2)](2) ((iPr)PCP) and C(6)H(4)[CH(2)P(tBu)(2)](2) ((tBu)PCP) are described. The chloride complex ((iPr)PCP)PtCl (6) and the unsaturated cationic complexes [(PCP)Pt](+)X(-) (X = OTf(-), BF(4)(-)) (1, 7), based on both PCP ligands, were prepared and the latter reacted with carbon monoxide to give the corresponding cationic carbonyl complexes [(PCP)Pt(CO)](+)X(-) (X = OTf(-), BF(4)(-)) (2, 8a). Hydride nucleophilic attack on both carbonyl complexes resulted in rare neutral platinum formyl complexes ((iPr)PCP)Pt(CHO) (3) and ((tBu)PCP)Pt(CHO) (9). Complex 3 undergoes decarbonylation to the corresponding hydride complex within hours at room temperature, while the bulkier complex 9 is more stable and undergoes complete decarbonylation only after 3-4 d. This observation demonstrates the very significant steric effect of the ligand on stabilization of the corresponding formyl complexes. Reaction of complex 9 with triflic acid resulted in the carbonyl complex [((tBu)PCP)Pt(CO)](+) OTf(-) (8b) with liberation of H(2), an unusual transformation for a metal formyl. Reaction with methyl triflate resulted in the Fischer carbene-type complex, the methoxy-methylidene [((tBu)PCP)Pt(CHOCH(3))](+)OTf(-) (11). The X-ray structures of complexes 2, 6, 8a and 11 were determined.     

Visible light-induced release of nitrogen monoxide from a nitrosylrhodium complex

The important roles that nitric oxide (NO) plays in biological environments, and the need for precise and targeted delivery of NO for medicinal and other purposes have led to intense research in the area of metal nitrosyl complexes as thermal and photochemical sources of NO. Complexes with a good combination of chemical stability and high quantum yield for photochemical release of NO upon irradiation with visible light in aqueous solutions are rare. Here we report that a simple macrocyclic nitrosylrhodium complex [L(2)(H(2)O)Rh(NO)](2+) (L(2)=Me(6)[14]aneN(4)) exhibits unique chemical and photochemical properties that make it an excellent photochemical precursor of NO. The complex is highly soluble in water, thermally stable, and resistant toward O(2). Irradiation in the 648 nm band generates NO and [L(2)(H(2)O)Rh](2+) in aqueous solutions with a quantum yield of 1.00±0.07, the highest ever reported for a nitrosyl complex under any conditions. In the absence of O(2), the two fragments combine to regenerate [L(2)(H(2)O)Rh- (NO)](2+), but in O(2)-containing solutions, [L(2)(H(2)O)RhOO](2+) is formed as determined in spectral and kinetic measurements. The kinetics of the reaction of this superoxo complex with NO were measured by laser flash photolysis, k=(3.9±0.4)×10(7) M(-1) s(-1). Steady-state photolysis of [L(2)(H(2)O)Rh(NO)](2+) under O(2) yielded [L(2)(H(2)O)Rh(ONO(2))](2+), a long-lived nitrato intermediate that can also be generated in a direct reaction between NO and genuine [L(2)(H(2)O)RhOO](2+). Thus, visible-light photolysis of the [L(2)(H(2)O)Rh(NO)](2+)/O(2) system converts it to the [L(2)(H(2)O)RhOO](2+)/NO combination.     

Reduction of nitrous acid with a macrocyclic rhodium complex that acts as a functional model of nitrite reductase

Nitrous acid reacts with L(2)(H(2)O)Rh(2+) (L(2) = meso-hexamethylcyclam) in acidic aqueous solutions to generate a strongly absorbing intermediate Int-1 (λ(max) 400 nm, ε = 1200 M(-1) cm(-1)). The reaction follows a mixed second order rate law with k = (6.9 ± 0.3) × 10(4) M(-1) s(-1), independent of [H(+)]. The lack of acid dependence shows that Int-1 is a rhodium(II) complex of HNO(2), most reasonably assigned as L(2)(H(2)O)Rh(HNO(2))(2+). This species is analogous to the early iron and copper intermediates in the reduction of nitrite by nitrite reductases and by deoxyhemoglobin. In the presence of excess L(2)(H(2)O)Rh(2+), the lifetime of Int-1 is about 1 min. It decays to a 1:1 mixture of L(2)(H(2)O)RhNO(2+) and L(2)Rh(H(2)O)(2)(3+) with kinetics that are largely independent of the concentration of excess L(2)(H(2)O)Rh(2+) and of [H(+)] at [H(+)] < 0.03 M. At [H(+)] > 0.03 M, an acid-catalyzed pathway becomes effective, suggesting protonation and dehydration of Int-1 to generate L(2)(H(2)O)RhNO(3+) (Int-2) followed by rapid reduction of Int-2 by excess L(2)(H(2)O)Rh(2+). Int-2, which was generated and characterized independently, is an analog of the electrophilic intermediates in the mechanism of biological reduction of nitrite to (?)NO. Excess nitrite greatly reduces the lifetime of Int-1, which under such conditions decomposes on a millisecond time scale by nitrite-catalyzed disproportionation to yield L(2)(H(2)O)RhNO(2+) and L(2)Rh(III). This reaction provides additional support for the designation of Int-1 as a Rh(II) species. The complex reaction mechanism and the detection of Int-1 demonstrate the ability of inorganic complexes to perform the fundamental chemistry believed to take place in the biological reduction of HNO(2) to NO catalyzed by nitrite reductases or deoxyhemoglobin.     

Formation of Trinuclear Rhodium‐Hydride Complexes [{Rh(PP*)H}3‐ (μ2‐H)3(μ3‐H)][anion]2—During Asymmetric Hydrogenation?

Recently described and fully characterized trinuclear rhodium‐hydride complexes [{Rh(PP*)H}₃(μ₂‐H)₃(μ₃‐H)][anion]₂ have been investigated with respect to their formation and role under the conditions of asymmetric hydrogenation. Catalyst–substrate complexes with mac (methyl (Z)‐ N‐acetylaminocinnamate) ([Rh(tBu‐BisP*)(mac)]BF₄, [Rh(Tangphos)(mac)]BF₄, [Rh(Me‐BPE)(mac)]BF₄, [Rh(DCPE)(mac)]BF₄, [Rh(DCPB)(mac)]BF₄), as well as rhodium‐hydride species, both mono‐([Rh(Tangphos)‐ H₂(MeOH)₂]BF₄, [Rh(Me‐BPE)H₂(MeOH)₂]BF₄), and dinuclear ([{Rh(DCPE)H}₂(μ₂‐H)₃]BF₄, [{Rh(DCPB)H}₂(μ₂‐H)₃]BF₄), are described. A plausible reaction sequence for the formation of the trinuclear rhodium‐hydride complexes is discussed. Evidence is provided that the presence of multinuclear rhodium‐hydride complexes should be taken into account when discussing the mechanism of rhodium‐promoted asymmetric hydrogenation.     

Reactivity of Xantphos-Type Rhodium Complexes Towards SF4: SF3 Versus SF2 Complex Generation

S−F-bond activation of sulfur tetrafluoride at [Rh(Cl)(^tBuxanPOP)] ( 1 ; ^tBuxanPOP=9,9-dimethyl-4,5-bis-(di-tert-butylphosphino)-xanthene) led to the formation of the cationic complex [Rh(F)(Cl)(SF₂)(^tBuxanPOP)][SF₅] ( 2 a ) together with trans-[Rh(Cl)(F)₂(^tBuxanPOP)] ( 3 ) and cis-[Rh(Cl)₂(F)(^tBuxanPOP)] ( 4 ) which both could also be obtained by the reaction of SF₅Cl with 1 . In contrast to that, the conversion of SF₄ at the methyl complex [Rh(Me)(^tBuxanPOP)] ( 5 ) gave the isolable and room-temperature stable cationic λ⁴-trifluorosulfanyl complex [Rh(Me)(SF₃)(^tBuxanPOP)][SF₅] ( 6 ). Treatment of 6 with the Lewis acids BF₃ or AsF₅ produced the dicationic difluorosulfanyl complex [Rh(Me)(SF₂)(^tBuxanPOP)][BF₄]₂ ( 8 a ) or [Rh(Me)(SF₂)(^tBuxanPOP)][AsF₆]₂ ( 8 b ), respectively. Refluorination of 8 a was possible with the use of dimethylamine giving [Rh(Me)(SF₃)(^tBuxanPOP)][BF₄] ( 9 ). A reaction of 6 with trichloroisocyanuric acid (TClCA) gave the fluorido complex [Rh(F)(Cl)(SF₂)(^tBuxanPOP)][Cl] ( 2 b ) together with chloromethane and SF₅Cl.