Complexes of copper(I) halides with bis (trimethylsilyl) acetylene

Александров, Г. Г.; Gol'ding, I. R.; Sterlin, S. R.; Sladkov, A. M.; Struchkov, Yu. T.; Garbuzova, I. A.; Aleksanyan, V. T.

doi:10.1007/bf00949643

Cited by 5 publications

(8 citation statements)

References 10 publications

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“…19,23 The Cu-C alkyne distances are similar for 1 (1.973(2), 1.984(2) Å) and 3 (1.952(2), 1.960(2) Å) and are within the range typical for copper(I) alkyne complexes, although the Cu-C alkyne distances in dimeric [(η 2 -Me 3 SiCtCSiMe 3 )Cu(µ-X)] 2 (X ) Cl, Br) are slightly longer. 25,30 In accordance with the IR spectroscopic results, alkyne binding to the metal ions results in a lengthening of the CtC bond from 1.208(3) Å in noncoordinated Me 3 SiCtCSiMe 3 26 to 1.243(3) Å in 1 (1.236(3) Å in 3), which is characteristic for η 2 coordination to copper(I). 15 In addition, a significant bending of the initially linear arrangement of the SiCtCSi entities in 1 as well as the CCtCC entities in 3 is observed (1, C1-C2-Si2 ) 163.…”

Section: Resultssupporting

confidence: 80%

“…The Cu−O bond lengths in 1 and 3 (1.987(1)−2.004(2) Å) are similar to those usually observed for μ-1,2,3,4 oxalato copper(II) compounds, and they are also comparable to the Cu−O bond lengths in alkyne-stabilized copper(I) carboxylates . With respect to the metric parameters of the oxalato group, complexes 1 and 3 are basically identical (Figures and ), and no significant differences could be found in comparison to the structural data of μ-1,2,3,4 oxalato bridges in copper(II) compounds described earlier. , The Cu−C alkyne distances are similar for 1 (1.973(2), 1.984(2) Å) and 3 (1.952(2), 1.960(2) Å) and are within the range typical for copper(I) alkyne complexes, although the Cu−C alkyne distances in dimeric [(η 2 -Me 3 SiC⋮CSiMe 3 )Cu(μ-X)] 2 (X = Cl, Br) are slightly longer. , In accordance with the IR spectroscopic results, alkyne binding to the metal ions results in a lengthening of the C⋮C bond from 1.208(3) Å in noncoordinated Me 3 SiC⋮CSiMe 3 to 1.243(3) Å in 1 (1.236(3) Å in 3 ), which is characteristic for η 2 coordination to copper(I) . In addition, a significant bending of the initially linear arrangement of the SiC⋮CSi entities in 1 as well as the CC⋮CC entities in 3 is observed ( 1 , C1−C2−Si2 = 163.2(2)°, C2−C1−Si1 = 170.5(2)° versus 179.1(2)° in free Me 3 SiC⋮CSiMe 3 ; 3 , C3−C4−C5 = 161.0(2)°, C4−C5−C6 = 161.9(2)°).…”

Section: Resultssupporting

confidence: 76%

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Dicopper(I) Oxalate Complexes Stabilized by Lewis Bases: Potential Precursors for Copper Deposition

et al. 2003

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The synthesis, characterization, and thermal behavior of the dicopper(I) oxalate complexes L 2 Cu 2 O 4 C 2 (L ) Me 3 SiCtCSiMe 3 (1), Me 3 SiCtC n Bu (2), EtCtCEt (3), H 2 CdC(H)SiMe 2 t Bu (4), H 2 CdC(H)SiEt 2 Me (5), norbornene ( 6)) is reported. All complexes can be prepared in a straightforward manner by the reaction of stoichiometric amounts of Cu 2 O and oxalic acid with 2 equiv of the respective alkyne or alkene. The complexes are stable at room temperature, and in solid form they can be handled in air for some time. Their thermal behavior was studied by thermal gravimetric analysis (TGA). The order of thermal stability was found to be 1 > 6 > 4 > 2 ≈ 3 > 5. Decomposition starts between 50 and 100 °C and is completed between 300 and 350 °C. All compounds fully decompose via an efficient internal redox process to give elemental copper, CO 2 , and the free alkyne or alkene ligands, which makes these new complexes promising precursors for copper deposition (in the case of 4, it is likely that H 2 CdC(H)SiMe 2 H and isobutene is formed via β-hydrogen elimination from H 2 CdC(H)SiMe 2 t Bu). Distinct two-or three-step decomposition sequences for the individual complexes are revealed by the TGA analyses and are discussed. The single-crystal X-ray structures of 1 and 3 are reported, which are the first for copper(I)/oxalato compounds. Both complexes exhibit the anticipated planar dinuclear structure with the oxalate in a µ-1,2,3,4 bridging mode and the alkynes or alkenes as capping ligands.

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Section: Resultssupporting

confidence: 80%

Section: Resultssupporting

confidence: 76%

Dicopper(I) Oxalate Complexes Stabilized by Lewis Bases: Potential Precursors for Copper Deposition

et al. 2003

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“…The asymmetric units of complexes 4a , b are comprised of two {Ag 2 (μ 2 -η 2 -ethyne-1,2-diyl)} units attached together by four bridging μ 2 -trifluoroacetate anions adopting the type F structure and are strictly comparable to the complexes [Cu 4 ({SiMe 3 } 2 (μ 2 -η 2 -CC))(μ 2 -O 2 CMe) 4 ], [Cu 4 ({Re(CO) 5 } 2 (μ 2 -η 2 -CC))(μ 2 -O 2 PF 2 ) 4 ], and [Cu 4 (Re(μ 2 -η 2 -CCSiMe 3 )(CO) 5 ) 2 (μ 2 -O 2 PF 2 ) 4 ] . The two Ag 2 (μ 2 -η 2 -ethyne-1,2-diyl) units are typical dimetallo tetrahedra (Ag 2 C 2 ) with average Ag–C bond lengths of 2.30(7) and 2.32(3) Å for 4a , b , respectively.…”

Section: Resultsmentioning

confidence: 99%

Anion-Directed Solid-State Structures of Copper(I) and Silver(I) Adducts of Ruthenium Ethyne-1,2-diyl Compounds

et al. 2015

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A number of group 11 salts, [MX] (M = Ag, X– = –O3SCF3, –O2CCF3, BF4 –; M = Cu; X = Cl, Br) and [Cu(MeCN)4][PF6], were found to react in varying stoichiometries with ethyne-1,2-diyl compounds, [{Ru(CO)2(η-C5H4R)}2(μ2-CC)] (R = H, Me), to give a number of complex cations. The trication salts [Ag3({Ru(CO)2(η-C5H4Me)}2(μ2-η1:η1-CC))3](O3SCF3)3, [Ag3({Ru(CO)2(η-C5H4R)}2(μ2-η1:η1-CC))({Ru(CO)2(η-C5H4R)}2(μ2-η1:η2-CC))2](BF4)3, and [Cu3({Ru(CO)2(η-C5H4R)}2(μ2-η1:η2-CC))({Ru(CO)2(η-C5H4R)}2(μ2-η2-CC))](PF6)3 result from the use of the respective anion salts in their syntheses. Coordination of Ag+ by the ethyne-1,2-diyl complexes in the presence of F3CCO2 – yields the tetranuclear complexes [Ag4({Ru(CO)2(η-C5H4R)}2(μ2-η2-CC))2](μ2-O2CCF3)4 (R = H, Me). The reaction of CuCl does not afford the discrete dimeric complexes normally observed for internal alkynes and metal alkynyl complexes but, rather, the 1-D polymer [Cu2(μ-Cl)2({Ru(CO)2(η-C5H4R)}2(η2-CC))](∞|∞), while CuBr gives the discrete dimer motif known in the literature. The solution structures at 1/2, 1/1, and 2/1 stoichiometries of Ag+/[{Ru(CO)2(η-C5H5)}2(μ2-CC)] have been probed spectroscopically, and the {Ru(CO)2(η-C5H4R)} environments appear to be equivalent and, likewise, the resonances attributable to their CC units. In a subsequent reaction of [{Ru(CO)2(η-C5H4R)}2(μ2-CC)] and AgBF4 use of a strict Ag+/ethyne-1,2-diyl ratio gave [Ag({Ru(CO)2(η-C5H5)}2(η2-CC))2](BF4). The analogous Cu+ adduct [Cu({Ru(CO)2(η-C5H5)}2(η2-CC))2](PF6) is observed, along with the tricopper(I) adduct from the reaction of [{Ru(CO)2(η-C5H4R)}2(μ2-CC)] and [Cu(NCMe)4](PF6). A combination of factors appears to control the solid-state structures of these coinage metal adducts, with the anion found to be that which influences the packing to the greatest extent.

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“…The Cu(1)−Br(1) bond length at 2.296(2) Å in compound 7b is decisively shorter than the according distances in other copper(I) bromide containing molecules [2.40−2.46 Å]. , As a result of the η 2 -coordination of the C⋮CSiMe 3 ligand to the copper atom the Ti(1)−C(11)−C(12) [167.5(8)°], as well as the C(11)−C(12)−Si(3) [165.0(8)°] units deviate from linearity. Thereby, the TiC⋮CSi entity is trans bent, which is typical for heterobimetallic compounds of the type {[Ti](C⋮CSiMe 3 ) 2 }CuR in which both alkynyl ligands are η 2 -bonded to a CuR moiety. − Through this deformation different copper-to-carbon bond lengths are observed [Cu(1)−C(11) = 2.012(9) Å and Cu(1)−C(12) = 2.102(8) Å; Table ].…”

Section: Resultsmentioning

confidence: 99%

“…The copper−bromine bond length at 2.296(2) Å is shorter than according distances in for example dimeric [η 2 -Me 3 SiC⋮CSiMe 3 )CuBr] 2 [2.407(1) Å] 2,23 or polymeric [CuBr] n [2.46 Å] . In fact for the η 1 -chloro and η 2 -alkyne interaction in combination with the geometric constraints of the mono(σ-alkynyl)titanocene chloride fragment in compound 7b a relative short Ti−Cu distance [2.958(3) Å] is observed. , …”

Section: Discussionmentioning

confidence: 99%

Reaction Chemistry of Alkynyl-Functionalized Titanocenes. X-ray Structure Analyses of (η⁵-C₅H₄SiMe₃)₂Ti(Cl)(CH₂SiMe₃) and [(η⁵-C₅H₄SiMe₃)₂Ti(Cl)(C⋮CSiMe₃)]CuBr

Lang

Frosch

et al. 1996

Inorg. Chem.

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The synthesis and reaction chemistry of the mono (σ-alkynyl) titanocene chlorides [Ti](Cl)(C⋮CR) {[Ti] = (η5-C5H4SiMe3)2Ti; 2a, R = Ph; 2b, R = SiMe3} is described. Treatment of compounds 2a and 2b with ClMgCH2SiMe3 or LiC⋮CR‘ yields [Ti](CH2SiMe3)(C⋮CSiMe3) (3) or [Ti](C⋮CR)(C⋮CR‘) (5a, R = Ph, R‘ = SiMe3; 5b, R = R‘ = Ph; 5c, R = R‘ = SiMe3), respectively. The reaction of compounds 2a, 2b, or 5a with polymeric [CuX] n (X = Cl, Br, I) produces the heterobimetallic titanium−copper complexes {[Ti](Cl)(C⋮CR)}CuX (6a, R = Ph, X = Cl; 6b, R = Ph, X = Br; 6c, R = Ph, X = I; 7a, R = SiMe3, X = Cl; 7b, R = SiMe3, X = Br) or {[Ti](C⋮CPh)(C⋮CSiMe3)}CuX (8a, X = Cl; 8b, X = Br). While compounds 2a and 2b do not react with [AgX] n (X = Cl, Br), it is found that the bis(σ-alkynyl)titanocene 5a is able to break down the polymeric structure of [AgX] n to produce the heterobimetallic compounds {[Ti](C⋮CPh)(C⋮CSiMe3)}AgX (10a, X = Cl; 10b, X = Br). Moreover, compound 8a can be synthesized by treatment of 2a or 2b with [CuC⋮CR‘] n (R‘ = SiMe3, Ph). However, when compound 3 is reacted with [CuCl] n under appropriate reaction conditions, the formation of {[Ti](C⋮CSiMe3)2}CuCl (9b), [CuCH2SiMe3]4, [Ti](Cl)(CH2SiMe3) (4), and [Ti]Cl2 (1) is observed; a reaction mechanism for the formation of the latter compounds is discussed. The solid state structures of [Ti](Cl)(CH2SiMe3) (4) and {[Ti](Cl)(C⋮CSiMe3)}CuBr (7b) were determined. Crystals of 4 and 7b are monoclinic, space group P21/n. 4: C20H37ClSi3Ti, cell constants a = 6.812(2) Å, b = 11.298(6) Å, c = 33.16(1) Å, β = 92.25(3)°, and Z = 4. 7b: C21H35BrClCuSi3Ti, cell constants a = 13.257(7) Å, b = 10.470(5) Å, c = 20.39(1) Å, β = 100.91(3)°, and Z = 4.

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Complexes of copper(I) halides with bis (trimethylsilyl) acetylene

Cited by 5 publications

References 10 publications

Dicopper(I) Oxalate Complexes Stabilized by Lewis Bases: Potential Precursors for Copper Deposition

Dicopper(I) Oxalate Complexes Stabilized by Lewis Bases: Potential Precursors for Copper Deposition

Anion-Directed Solid-State Structures of Copper(I) and Silver(I) Adducts of Ruthenium Ethyne-1,2-diyl Compounds

Reaction Chemistry of Alkynyl-Functionalized Titanocenes. X-ray Structure Analyses of (η⁵-C₅H₄SiMe₃)₂Ti(Cl)(CH₂SiMe₃) and [(η⁵-C₅H₄SiMe₃)₂Ti(Cl)(C⋮CSiMe₃)]CuBr

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Complexes of copper(I) halides with bis (trimethylsilyl) acetylene

Cited by 5 publications

References 10 publications

Dicopper(I) Oxalate Complexes Stabilized by Lewis Bases: Potential Precursors for Copper Deposition

Dicopper(I) Oxalate Complexes Stabilized by Lewis Bases: Potential Precursors for Copper Deposition

Anion-Directed Solid-State Structures of Copper(I) and Silver(I) Adducts of Ruthenium Ethyne-1,2-diyl Compounds

Reaction Chemistry of Alkynyl-Functionalized Titanocenes. X-ray Structure Analyses of (η5-C5H4SiMe3)2Ti(Cl)(CH2SiMe3) and [(η5-C5H4SiMe3)2Ti(Cl)(C⋮CSiMe3)]CuBr

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Reaction Chemistry of Alkynyl-Functionalized Titanocenes. X-ray Structure Analyses of (η⁵-C₅H₄SiMe₃)₂Ti(Cl)(CH₂SiMe₃) and [(η⁵-C₅H₄SiMe₃)₂Ti(Cl)(C⋮CSiMe₃)]CuBr