Cuprous tert-butoxide. New and useful metalation reagent

Tsuda, Tetsuo; Hashimoto, Toshiaki; Saegusa, Takeo

doi:10.1021/ja00757a069

Cited by 167 publications

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“…[1] However, information on the structures and properties of donor-free coinage metal(I) alkoxides and silyl oxides is still sparse and so far limited to Cu. [2][3][4][5][6][7][8] Several of these homoleptic Cu I alkoxides and silyl oxides were successfully tested for chemical vapor deposition (CVD) processes. [6,9] Of the Cu I alkoxides and silyl oxides, only CuOCR 3 and CuOSiR 3 (R = CH 3 and C 6 H 5 ) have been structurally characterized.…”

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AgOC(CF₃)₃ and AgOSiiPr₃—Synthesis and Characterization of a Donor‐Free Silver(I) Alkoxide and Silyl Oxide

Reisinger¹,

Himmel²,

Krossing³

2006

Angew Chem Int Ed

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“…Although donor-free copper(I) alkoxides and silyl oxides have been known for a long time, [3] no homologous compounds with silver or gold have been reported, with the exception of two phosphane adducts. [2,15] However, homoleptic Ag I alkoxides and silyl oxides might, analogously to the copper compounds, be versatile reagents in organometallic synthesis.…”

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AgOC(CF₃)₃ and AgOSiiPr₃—Synthesis and Characterization of a Donor‐Free Silver(I) Alkoxide and Silyl Oxide

Reisinger¹,

Himmel²,

Krossing³

2006

Angew Chem Int Ed

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“…In the course of these investigations we attempted to prepare CuOtBu using an alternative procedure to the ones reported by Weiss et al and Saegusa et al [2] Our reaction of KOtBu with copper(i) chloride in THF at room temperature afforded a dark green solution together with a red precipitate.…”

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“…Because of the green color and the deposition of copper during the reaction it was assumed that disproportion had resulted in a mixture of copper(i/ii) alkoxides or Cu(OtBu) 2 . [2] The true nature of these species only became apparent once structurally characterized by X-ray crystallography. [13] Because 1 b has similar structural parameters, only the structural data for 1 a are discussed (Figure 1 (5) and are similar to KÀO bond lengths observed in other potassium alkoxide complexes.…”

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Template Synthesis and Theoretical Investigation of [Cu^II₂Cu^I₃K₆(μ₆‐Cl)(μ₃‐OtBu)₁₂]: The First Mixed‐Valence Copper Alkoxide

et al. 2003

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“…t-BuOCu is one of the very few examples of thermally stable copper (I) alkoxides which has been found to be an efficient reagent of metalation ( organocopper formation). 2 …”

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Vinyl Polymerization by Copper (I) tert-Butoxide

Sàegusa

Horiguchi

Tsuda

1976

Polym J

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ABSTRACT:This paper describes the catalyst character of copper (I) tert-butoxide (t-BuOCu) for vinyl polymerization. At the low temperature of 0°C, t-BuOCu initiated the anionic polymerization of acrylonitrile (AN) in the presence of a coordinating compound such as tert-butyI isocyanide (t-BuNC), trimethyl phosphite, triphenylphosphine, and hexamethylphosphoric triamide (HMPT). The mechanism of the anionic polymerization was shown by the reaction of AN monomer with t-BuOCu-t-BuNC in the presence of a protic solvent of tert-BuOH and by copolymerization experiments. Without any coordinating compound, t-BuOCu caused the polymerization of styrene (ST), methyl acrylate (MA), methyl methacrylate (MMA), and AN at the higher temperature of 80°C, where a radical mechanism was assumed.KEY WORDS Vinyl Polymerization / t-BuOCu / Ligand / Anionic Mechanism / Organocopper / Acrylonitrile / t-BuNC / Phosphine / HMPT / Copolymerization / In a previous paper,1 vinyl polymerization by the cyclopentadienylcopper (I)-tert-butyl isocyanide complex ((CPD)Cu, t-BuNC) was reported. This complex alone did not induce the polymerization, but became highly effective for the polymerization when excess t-BuNC was added. In this polymerization, the organocopper (I) complex was assumed to be the propagating species. The results of both homopolymerization and copolymerization by (CPD)Cu,(t-BuNC)2 were different from those of the conventional anionic polymerizations by the catalysts of organolithium and organomagnesium. This paper describes the vinyl polymerization by t-BuOCu. t-BuOCu is one of the very few examples of thermally stable copper (I) alkoxides which has been found to be an efficient reagent of metalation ( organocopper formation). 2 RESULTS AND DISCUSSIONVinyl Polymerization by t-BuOCu t-BuOCu was prepared from the reaction of tert-BuOLi with CuCl, which was purified by sublimation. 2 At 0°C, t-BuOCu alone did not induce the vinyl polymerization, but AN was polymerized when t-BuNC was added to t-BuOCu. Table I shows the effect of added t-BuNC on the 302 conversion and molecular weight of the product polymer. About an equimolar amount of t-BuNC to t-BuOCu was required to activate t-BuOCu. Larger excess of t-BuNC did not much affect either the conversion or the molecular weight of the product polymer. Under the present experimental conditions, the best conversion was obtained when the ratio of t-BuNC to t-BuOCu was 2. As for the vinyl polymerization by the system of t-BuOCu-t-BuNC, it should be mentioned that an isolated species of t-BuOCu, tBuNC complex, which was prepared from an equimolar mixture of t-BuOCu and t-BuNC, has • t-BuOCu, 0.20 mmol; AN, 76 mmol; toluene, 10.0 ml; polymerization at 0°C for 3 hr.

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Cuprous tert-butoxide. New and useful metalation reagent

Abstract: Lowe, and T. J. Moulson for helpful discussions and Mr. E. S . Greenberg for computational assistance. distance.(10) pn = (r2)/R3; pl = (r4)/R5, where R is the metal to point charge

Cited by 167 publications

References 0 publications

AgOC(CF₃)₃ and AgOSiiPr₃—Synthesis and Characterization of a Donor‐Free Silver(I) Alkoxide and Silyl Oxide

AgOC(CF₃)₃ and AgOSiiPr₃—Synthesis and Characterization of a Donor‐Free Silver(I) Alkoxide and Silyl Oxide

Template Synthesis and Theoretical Investigation of [Cu^II₂Cu^I₃K₆(μ₆‐Cl)(μ₃‐OtBu)₁₂]: The First Mixed‐Valence Copper Alkoxide

Vinyl Polymerization by Copper (I) tert-Butoxide

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Cuprous tert-butoxide. New and useful metalation reagent

Abstract: Lowe, and T. J. Moulson for helpful discussions and Mr. E. S . Greenberg for computational assistance. distance.(10) pn = (r2)/R3; pl = (r4)/R5, where R is the metal to point charge

Cited by 167 publications

References 0 publications

AgOC(CF3)3 and AgOSiiPr3—Synthesis and Characterization of a Donor‐Free Silver(I) Alkoxide and Silyl Oxide

AgOC(CF3)3 and AgOSiiPr3—Synthesis and Characterization of a Donor‐Free Silver(I) Alkoxide and Silyl Oxide

Template Synthesis and Theoretical Investigation of [CuII2CuI3K6(μ6‐Cl)(μ3‐OtBu)12]: The First Mixed‐Valence Copper Alkoxide

Vinyl Polymerization by Copper (I) tert-Butoxide

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AgOC(CF₃)₃ and AgOSiiPr₃—Synthesis and Characterization of a Donor‐Free Silver(I) Alkoxide and Silyl Oxide

AgOC(CF₃)₃ and AgOSiiPr₃—Synthesis and Characterization of a Donor‐Free Silver(I) Alkoxide and Silyl Oxide

Template Synthesis and Theoretical Investigation of [Cu^II₂Cu^I₃K₆(μ₆‐Cl)(μ₃‐OtBu)₁₂]: The First Mixed‐Valence Copper Alkoxide