Cationic transition-metal complexes. Part II. The reaction of arenes and olefins with bis(cyclo-octa-1,5-diene or norbornadiene)rhodium tetrafluoroborate

Green, M.; Kuc, T. A.

doi:10.1039/dt9720000832

Cited by 58 publications

(29 citation statements)

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“…[23,24] Based on IR spectroscopic data and their lability in solution, these com- plexes were believed to have O-bound DMSO ligands. To ascertain the exact structure of these compounds, we synthesized complex [Rh(cod)(DMSO) 2 ]BF 4 (11) and characterized it by X-ray crystallogrphy.…”

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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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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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“…It is interesting to note that the [(C 4 Et 4 )Rh] + fragment prefers η 6 -coordination with 4methylaniline in contrast to the related [(nbd)Rh] + fragment, which forms a complex with N-coordinated aniline [(nbd)Rh-(C 6 H 5 NH 2 ) 2 ] + . 13 Finally, we tried to synthesize cyclobutadiene iridium complexes using our general approach. Treatment of [(coe) 2 IrCl] 2 with AgPF 6 and p-xylene gave the expected complex [(coe) 2 Ir(p-xylene)] + (4) in 64% yield (Scheme 3).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Cyclobutadiene Arene Complexes of Rhodium and Iridium

et al. 2016

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Reactions of [(C2H4)2RhCl]2 or [(coe)2RhCl]2 (coe = cyclooctene) with AgPF6 and arenes, followed by addition of 3-hexyne, give the cyclobutadiene complexes [(C4Et4)Rh(arene)]+ in 40–65% yield (arene = tert-butylbenzene, p-xylene, mesitylene, 4-mesitylbutanoic acid). In the absence of arenes, the hexaethylbenzene complex [(C4Et4)Rh(C6Et6)]+ is formed in 70% yield as a result of cyclotrimerization of 3-hexyne in the coordination sphere of rhodium. Similar reaction of [(coe)2IrCl]2 with AgPF6 and 3-hexyne leads to [(C4Et4)Ir(C6Et6)]+, which is apparently the first reported cyclobutadiene iridium complex. DFT calculations suggest that formation of the model cyclobutadiene complex [(C4Me4)Rh(C6H6)]+ from bis(alkyne) intermediate [(C2Me2)2Rh(C6H6)]+ can proceed via a metallacycle transition state with a low energy barrier of 14.5 kcal mol–1.

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“…Also relevant here is that for [Rh(diene)L,lf complexes, n may be 3 for NBD, but only 2 for COD systems (13). The stronger n: back-bonding properties of NBD have been invoked to rationalize the reactivity patterns (18). Infrared data for all of the complexes reported here show that the anions are uncoordinated, since only the characteristic bands of PF6-and SbF,-are observed at 840 vs, 560 s, and 658 vs, 290 s cm-l, respectively (19 9s-CH2 resonance obscured.…”

Section: Acetone Cotnplexesmentioning

confidence: 97%

Cationic rhodium(I) sulfoxide complexes. Synthesis and spectroscopic properties

James¹,

Morris²,

Reimer³

1977

Can. J. Chem.

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. Can. J. Chem. 55,2353Chem. 55, (1977. I1 semble que le diary1 sulfoxyde se coordonne en solution mais on n'a pu isoler aucun compose solide. Les dkplacements vers les hauts champs de rksonances du sulfoxyde (rmn 'H) suggtrent qu'il y a un blindage par les groupes phknyles adjacents du PPh,; par ailleurs la diminution de la valeur de v(S0) par coordination indique qu'il y a formation de lien avec l'oxygtne dans tous les cas. Des donnCes infrarouges indiquent que le dkplacement de la frkquence v(S0) par coordination avec I'oxygkne est approximativement proportionnel avec la force du lien mktal/oxygtne par un ktendue de complexes de mktaux de transition et de DMSO et TMSO.[Traduit par le journal]

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Cationic transition-metal complexes. Part II. The reaction of arenes and olefins with bis(cyclo-octa-1,5-diene or norbornadiene)rhodium tetrafluoroborate

Cited by 58 publications

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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)

Cyclobutadiene Arene Complexes of Rhodium and Iridium

Cationic rhodium(I) sulfoxide complexes. Synthesis and spectroscopic properties

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Cationic transition-metal complexes. Part II. The reaction of arenes and olefins with bis(cyclo-octa-1,5-diene or norbornadiene)rhodium tetrafluoroborate

Cited by 58 publications

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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)

Cyclobutadiene Arene Complexes of Rhodium and Iridium

Cationic rhodium(I) sulfoxide complexes. Synthesis and spectroscopic properties

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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)