Cationic transition-metal complexes. Part I. Synthesis and reactions of bis(diene)-rhodium and -iridium tetrafluoroborates

Green, M.; Kuc, T. A.; Taylor, Susan H.

doi:10.1039/j19710002334

Cited by 148 publications

(68 citation statements)

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“…Work with AgPF 6 was performed in the absence of light. The complexes [Rh 2 Cl 2 (coe) 4 ], [39] [Rh 2 Cl 2 (cod) 2 ], [40] [Rh(cod) 2 ]BF 4 , [41] [Rh(coe) 2 (OCMe 2 ) 2 ]PF 6 , [27] [Ir 2 Cl 2 (coe) 4 ], [42] and [Ir(coe) 2 (OCMe 2 ) 2 ]PF 6 , [28] were prepared according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)

Dorta

Rozenberg

Shimon

et al. 2003

Chemistry A European J

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Novel neutral and cationic Rh(I) and Ir(I) complexes that contain only DMSO molecules as dative ligands with S-, O-, and bridging S,O-binding modes were isolated and characterized. The neutral derivatives [RhCl(DMSO)(3)] (1) and [IrCl(DMSO)(3)] (2) were synthesized from the dimeric precursors [M(2)Cl(2)(coe)(4)] (M=Rh, Ir; COE=cyclooctene). The dimeric Ir(I) compound [Ir(2)Cl(2)(DMSO)(4)] (3) was obtained from 2. The first example of a square-planar complex with a bidentate S,O-bridging DMSO ligand, [(coe)(DMSO)Rh(micro-Cl)(micro-DMSO)RhCl(DMSO)] (4), was obtained by treating [Rh(2)Cl(2)(coe)(4)] with three equivalents of DMSO. The mixed DMSO-olefin complex [IrCl(cod)(DMSO)] (5, COD=cyclooctadiene) was generated from [Ir(2)Cl(2)(cod)(2)]. Substitution reactions of these neutral systems afforded the complexes [RhCl(py)(DMSO)(2)] (6), [IrCl(py)(DMSO)(2)] (7), [IrCl(iPr(3)P)(DMSO)(2)] (8), [RhCl(dmbpy)(DMSO)] (9, dmbpy=4,4'-dimethyl-2,2'-bipyridine), and [IrCl(dmbpy)(DMSO)] (10). The cationic O-bound complex [Rh(cod)(DMSO)(2)]BF(4) (11) was synthesized from [Rh(cod)(2)]BF(4). Treatment of the cationic complexes [M(coe)(2)(O=CMe(2))(2)]PF(6) (M=Rh, Ir) with DMSO gave the mixed S- and O-bound DMSO complexes [M(DMSO)(2)(DMSO)(2)]PF(6) (Rh=12; Ir=in situ characterization). Substitution of the O-bound DMSO ligands with dmbpy or pyridine resulted in the isolation of [Rh(dmbpy)(DMSO)(2)]PF(6) (13) and [Ir(py)(2)(DMSO)(2)]PF(6) (14). Oxidative addition of hydrogen to [IrCl(DMSO)(3)] (2) gave the kinetic product fac-[Ir(H)(2)Cl(DMSO)(3)] (15) which was then easily converted to the more thermodynamically stable product mer-[Ir(H)(2)Cl(DMSO)(3)] (16). Oxidative addition of water to both neutral and cationic Ir(I) DMSO complexes gave the corresponding hydrido-hydroxo addition products syn-[(DMSO)(2)HIr(micro-OH)(2)(micro-Cl)IrH(DMSO)(2)][IrCl(2)(DMSO)(2)] (17) and anti-[(DMSO)(2)(DMSO)HIr(micro-OH)(2)IrH(DMSO)(2)(DMSO)][PF(6)](2) (18). The cationic [Ir(DMSO)(2)(DMSO)(2)]PF(6) complex (formed in situ from [Ir(coe)(2)(O=CMe(2))(2)]PF(6)) also reacts with methanol to give the hydrido-alkoxo complex syn-[(DMSO)(2)HIr(micro-OCH(3))(3)IrH(DMSO)(2)]PF(6) (19). Complexes 1, 2, 4, 5, 11, 12, 14, 17, 18, and 19 were characterized by crystallography.

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Section: Methodsmentioning

confidence: 99%

Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)

Dorta

Rozenberg

Shimon

et al. 2003

Chemistry A European J

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“…Among them, a combination of [IrCl(cod)] 2 and dppe, dppp or dppb was recognized to be the best catalyst for achieving high yields and high selectivities (entries [13][14][15]. Analogous catalysts prepared from a cationic iridium(I) precursor also predominated the formation of 2, but they were less selective than were neutral complexes (entries [17][18][19][20][21][22][23][24].…”

mentioning

confidence: 99%

Iridium-catalyzed hydroboration of alkenes with pinacolborane

et al. 2004

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Abstract-Hydroboration of terminal and internal alkenes with pinacolborane (1.2 equivalents) was carried out at room temperature in the presence of an iridium(I) catalyst (3 mol%). Addition of dppm (2 equivalents) to [Ir(cod)Cl] 2 gave the best catalyst for hydroboration of aliphatic terminal and internal alkenes at room temperature, resulting in addition of the boron atom to the terminal carbon of 1-alkenes with more than 99% selectivities. On the other hand, a complex prepared from dppe (2 equivalents) and [Ir(cod)Cl] 2 resulted in the best yields for vinylarenes such as styrene.These complexes exhibited higher levels of catalyst activity and selectivity than those of corresponding rhodium complexes.

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“…[3] Analysis of 2g and 3f by 31 P NMR spectroscopy showed chemical shifts identical to those observed for 3a and 4a. [3,26] was not feasible, as decomposition of the borate anions was observed during attempts to prepare bis-cyclooctadiene complexes from [Rh(COD)Cl] 2 , cyclooctadiene and Na [X] or Ag [X].…”

Section: Synthesis and Fluorous Biphasic Separation Of Rhodium Complementioning

confidence: 95%

“…Hexane, tetrahydrofuran (THF) and diethyl ether (Et 2 O) were distilled from sodium benzophenone ketyl, CH 2 Cl 2 from CaH 2 , acetone from CaCl 2 and toluene from sodium. FC-75 and a,a,a-trifluorotoluene were degassed and stored over molecular sieves (3 [Rh(COD) 2 ]BF 4 , [26] [Rh(COD)(acac)], [30] [Rh(COD)(dppb)]BF 4 (1a), [31] [Rh(COD)(dppb)][BPh 4 ] (1b), [17c] [Rh(COD)(Ar 2 PCH 2 -CH 2 PAr 2 )]BF 4 {Ar C 6 H 4 [SiMe(CH 2 CH 2 C 6 F 13 ) 2 ]-4 (3a) or C 6 H 4 [Si(CH 2 CH 2 C 6 F 13 ) 3 ]-4 (4a)} [3] were prepared according to literature procedures. All other chemicals were used as received.…”

Section: Experimental Section Generalmentioning

confidence: 99%

Enhanced Hydrogenation Activity and Recycling of Cationic Rhodium Diphosphine Complexes through the Use of Highly Fluorous and Weakly‐Coordinating Tetraphenylborate Anions

Broeke

Wolf

Deelman³

et al. 2003

Adv Synth Catal

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The effect of the nature of the anion on the performance of ionic rhodium catalysts has received little attention. Herein it is shown that the use of highly fluorous tetraphenylborate anions can enhance catalyst activity in both conventional and fluorous media. À (1 g)} the activity towards the hydrogenation of 1-octene in acetone increased in the order 1c < 1b < 1e < 1a < 1d~1f < 1g with 1g being twice as active as the commonly applied 1a. Despite the fluorophilic character introduced by the substituted tetraarylborate anions, the presence of some perfluoroalkyl-substituents in the cation was still required for achieving high partition coefficients. À (2g)} were prepared, which were active in the hydrogenation of 1-octene, 2g even more so than 3f. Both these highly fluorous catalysts could be recycled with 99% efficiency through fluorous biphasic separation, whereas the corresponding BF 4 À complex of 2g (2a) did not show any affinity for the fluorous phase.

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Cationic transition-metal complexes. Part I. Synthesis and reactions of bis(diene)-rhodium and -iridium tetrafluoroborates

Cited by 148 publications

References 0 publications

Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)

Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)

Iridium-catalyzed hydroboration of alkenes with pinacolborane

Enhanced Hydrogenation Activity and Recycling of Cationic Rhodium Diphosphine Complexes through the Use of Highly Fluorous and Weakly‐Coordinating Tetraphenylborate Anions

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Cationic transition-metal complexes. Part I. Synthesis and reactions of bis(diene)-rhodium and -iridium tetrafluoroborates

Cited by 148 publications

References 0 publications

Dimethylsulfoxide as a Ligand for RhI and IrI Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH3)

Dimethylsulfoxide as a Ligand for RhI and IrI Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH3)

Iridium-catalyzed hydroboration of alkenes with pinacolborane

Enhanced Hydrogenation Activity and Recycling of Cationic Rhodium Diphosphine Complexes through the Use of Highly Fluorous and Weakly‐Coordinating Tetraphenylborate Anions

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Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)

Dimethylsulfoxide as a Ligand for Rh^I and Ir^I Complexes—Isolation, Structure, and Reactivity Towards XH Bonds (X=H, OH, OCH₃)