Preparation of highly reactive metal powders. Direct reaction of nickel, cobalt, and iron metal powders with arene halides

Kavaliunas, Arunas V.; Rieke, Reuben D.

doi:10.1021/ja00538a058

Cited by 40 publications

(8 citation statements)

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“…Fifty years ago, Chatt and Shaw reported the synthesis of a range of four-coordinate phosphine-stabilised Ni(II) and Pt(II) complexes, 51 the compounds featuring ortho-substituted aryls being more stable. The use of highly reactive Rieke metals has also facilitated the formation of diaryl complexes of nickel, amongst others, such as M(C 6 F 5 ) 2 (M = Fe, Co, Ni) are synthesised via the reaction between the activated metal and C 6 F 5 I; 52 (23). 53 The dipentafluorophenylnickel complex coordinated by ligands such as 2,2¢-bipyridine, THF and carbon monoxide has also been crystallographically characterised.…”

Section: And Which Feature Quadruple Bonds Between the Metals 32mentioning

confidence: 99%

Recent developments in transition metal diaryl chemistry

Kays

2011

Dalton Trans.

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This Perspective discusses the synthesis and reactivity of low-coordinate transition metal diaryl complexes. The development of sterically demanding ligands, in particular m-terphenyls is facilitating the isolation of complexes featuring two-coordinate open-shell transition metal centres. These coordinatively unsaturated complexes are now being investigated for their reaction chemistry, which is not only contributing to the elucidation of the structure and bonding within these systems but is also leading to the formation of novel compounds.

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Section: And Which Feature Quadruple Bonds Between the Metals 32mentioning

confidence: 99%

Recent developments in transition metal diaryl chemistry

Kays

2011

Dalton Trans.

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“…cis-Pt(PEt 3 ) 2 (R)X (R ) alkyl or aryl) and cis-PtR 2 L 2 (R ) CH 3 or Ph; L ) sulfoxide or thioether). 760 The homoleptic nickel aryl complexes NiMes 2 594 and Ni(C 6 F 5 ) 5 761 have been described, but neither species has been isolated from solution and their structure and magnetic properties are unknown.…”

Section: Viii72 Lower Coordination Systemsmentioning

confidence: 99%

“…The homoleptic nickel aryl complexes NiMes 2 594 and Ni(C 6 F 5 ) 5 have been described, but neither species has been isolated from solution and their structure and magnetic properties are unknown.…”

Section: Viii72 Lower Coordination Systemsmentioning

confidence: 99%

Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure

1996

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“…[32] Rieke and Kavaliunas have shown the formation of metallic nickel by the reduction of nickel halides with lithium and naphthalene as an electron carrier, and this active nickel was effective in the coupling of benzylic halides and polyhalides. [33] They have demonstrated that this reactive nickel can react at near room temperature with one equivalent of iodopentafluorobenzene [34] and the resulting solution contained a mixture of the solvated species NiA C H T U N G T R E N N U N G (C 6 F 5 ) 2 and NiI 2 . It is important to note that in all of the above cases the reactions require a large excess of reducing agent and often an equimolar amount of nickel complex compared to the halogenated aromatic substrate.…”

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Nickel‐Catalyzed Coupling of Aryl Bromides in the Presence of Alkyllithium Reagents

Jhaveri¹,

Carter²

2008

Chemistry A European J

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Transition-metal-catalyzed coupling reactions of halogenated molecules leading to formation of new carbon-carbon bonds are a very important category of reactions used in the synthesis of complex compounds and conjugated polymers. [1][2][3] Within the past decade, this methodology has evolved into a powerful synthetic tool for the preparation of a wide range of specialty polymers, composite materials, and pharmaceutically active compounds both in the laboratory and on the industrial scale. It is also widely appreciated in the context of parallel synthesis and combinational chemistry. [4,5] We desired to develop an improved catalytic method for transition-metal-catalyzed aryl coupling reactions and report herein the one-pot, one-step, nickel-catalyzed coupling of aryl bromides in the presence of alkyllithium reagents [Eq. (1)].Metallic reagents including palladium and nickel complexes have demonstrated to be quite effective in C À C coupling reactions. Typically, coupling reactions of aryl halides involving the use of catalytic amounts of nickel(II) complexes require the addition of either magnesium or zinc to facilitate efficient coupling and regeneration of active nickel(0) catalytic species. For example, Kumada coupling reactions use magnesium for the formation of active alkyl/ aryl magnesium bromide species (Grignard formation), which is generally a substrate-and solvent-specific reaction (working optimally in tetrahydrofuran or diethyl ether as solvents). [6][7][8][9][10] Nickel reactions facilitated by the addition of zinc powder have been utilized in a similar fashion in organic synthesis, [11][12][13] as well as in efficient condensation polymerizations. [14][15][16] These reactions are not always well controlled, require prolonged heating at high temperatures, and the products have high levels of metal impurities that can be difficult and costly to remove. This trace-metal contamination is especially problematic if the end use is in pharmaceutical or microelectronic applications in which safety, performance, and reliability require stringent control of purity. Another known aryl-halide coupling reaction involves the use of highly reactive zinc (Rieke zinc), which is prepared by reduction of ZnCl 2 with lithium naphthalenide and has been shown to readily undergo oxidative addition with alkyl, aryl, and vinyl halides under mild conditions to generate the corresponding organozinc compounds. These reactive organozinc compounds are then cross-coupled with other aryl or vinyl halides using palladium(0) catalysts. [17] Recently, homocoupling of bromide compounds has been facilitated through the combination of metallic magnesium and a catalytic amount of iron salts.[18] Coupling reactions involving activated dihalogenated thiophene molecules catalyzed by nickel(II) complexes have also been demonstrated in the presence of reactive zinc (Rieke zinc) [19] or an alkylmagnesium reagent (GRIM/McCullough method) [20] to form regioregular polythiophenes.Coupling reactions of halogenated molecules involving nickel(0) compl...

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Preparation of highly reactive metal powders. Direct reaction of nickel, cobalt, and iron metal powders with arene halides

Cited by 40 publications

References 1 publication

Recent developments in transition metal diaryl chemistry

Recent developments in transition metal diaryl chemistry

Open-Shell Organometallics as a Bridge between Werner-Type and Low-Valent Organometallic Complexes. The Effect of the Spin State on the Stability, Reactivity, and Structure

Nickel‐Catalyzed Coupling of Aryl Bromides in the Presence of Alkyllithium Reagents

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