Synthesis of Cu(II) aminoalkoxide complexes and their unusual thermolysis to Cu(0)

Park, Jung‐Woo; Jang, Hong Suk; Kim, Minchan; Sung, Kiwhan; Lee, Su Yeon; Chung, Taek; Koo, Sang Man; Kim, Chang Gyoun; Kim, Yunsoo

doi:10.1016/j.inoche.2003.12.022

Cited by 28 publications

(7 citation statements)

References 32 publications

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“…Complex 2 may not cause the formation of a three-membered ring via addition of an Ir−C bond to a CC bond, which differs from the reaction of the Rh complex. Since 2 does not undergo β -hydrogen elimination either, the reaction at higher temperature produces the olefin or diene, whose formation is induced by γ -hydrogen elimination of the 2,2-dialkyl-3-butenyl ligand, as shown in Scheme . γ -Hydrogen of a 2-phenylethyl group is abstracted by the Ir center to form the four-membered metallacycle including an Ir(III) center.…”

Section: Resultsmentioning

confidence: 99%

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

et al. 2004

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2,2-Bis(2-phenylethyl)-1-methylenecyclopropane reacts with RhH(CO)(PPh 3 ) 3 at room temperature and with IrH(CO)(PPh 3 ) 3 at 70 °C to form the 3-butenyl complexes of these metals, M{η 1 :η 2 -CH 2 C(CH 2 CH 2 Ph) 2 CHdCH 2 }(CO)(PPh 3 ) 2 (1, M ) Rh; 2, M ) Ir). Heating 1 at 55 °C liberates 1,1-bis(2-phenylethyl)-1,3-butadiene, while the thermal reaction of 2 at 110 °C forms a mixture of 3-methyl-3-vinyl-1,5-diphenyl-1-pentene (48% NMR yield) and 3-methyl-3-vinyl-1,5-diphenylpentane (15% NMR yield). The reactions of excess amounts of 2,2-bis(2-phenylethyl)-1-methylenecyclopropane with RhH(CO)(PPh 3 ) 3 at 55 °C and with IrH-(CO)(PPh 3 ) 3 at 115 °C afford the alkenyl complexes trans-Rh{ 4), respectively. The reaction mechanisms are discussed on the basis of the results of the reactions under different conditions. HCtCC(CH 2 CH 2 Ph) 2 CH 3 reacts with MH(CO)(PPh 3 ) 3 (M ) Rh, Ir) to afford the alkynyl complexes trans-M{CtCC(CH 2 CH 2 Ph) 2 CH 3 }(CO)(PPh 3 ) 2 (5, M ) Rh; 6, M ) Ir) via oxidative addition of the C(alkyne)-H bond to the metal center and subsequent elimination of H 2 .

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Section: Resultsmentioning

confidence: 99%

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

et al. 2004

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“…Two alkoxides examples are: bis(dimethylamino-2-methyl-2-propanolato)copper(II) (BESHUD) [18] with the two Cu--O bond lengths at 1.864 Å and bis(9-(2-pyridyl)fluoren-9-olato-N,O)copper(II) methanol solvate (LIVFAY) [19] with the two Cu--O bond lengths at 1.911 and 1.912 Å . These shorter bonds are to be ascribed partly to the fact that the alcoholate is part of a N-containing chelating ligand and that in this case the coordination number is 4, as there are no axial ligands present.…”

Section: Metal Alcohol and Alkoxide Systemsmentioning

confidence: 99%

Metal-ligand bond lengths and strengths: are they correlated? A detailed CSD analysis

Nimmermark¹,

Öhrström²,

Reedijk³

2013

Zeitschrift für Kristallographie - Crystalline Materials

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Abstract. Structure data on metal-alkoxides, metal-alcohol, metal-carboxylates, metal-carboxylic acid, metal-azolate and metal-azole coordination compounds from the Cambridge Structural Database (CSD) were analysed in terms of bond lengths. In general the anionic ligands form shorter metal-ligand bonds by about 0.02-0.05 Å compared to neutral ligands, a clear indication of a charge contribution to the bonding interactions. This small difference is not, however, deemed as sufficient to generate two distinct classes of metal-ligand bonding. Instead, the anionic ligands can be viewed as having "charge assisted" metalligand bonding, corresponding to the same term used for "charge-assisted hydrogen bonding".

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“…Copper compounds remain a subject of research due to the importance of copper as an interconnect material in microelectronics . Copper is easily reduced to a metallic film, and this has led to an abundance of copper precursors, including β-diketonates, β-diketiminates, amidinates, guanidinates, aminoalkoxides, and pyrrolylaldiminates, to name a few.…”

Section: Introductionmentioning

confidence: 99%

Study of Monomeric Copper Complexes Supported by N-Heterocyclic and Acyclic Diamino Carbenes

et al. 2017

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The thermal properties of a series of monomeric copper(I) hexamethyldisilazide complexes supported by N-heterocyclic and acyclic diamino carbenes were evaluated to study the impact of N-alkyl substituents and backbone character on volatility and thermal stability of copper amides. The series of complexes were either liquids or solids with melting points in the broad range of 45−184 °C. Vaporization rates were measured by stepped-isothermal TGA experiments and found to be between 110−170 °C. Enthalpies of vaporization were determined to be 63−90 kJ/mol. Temperatures for 1 Torr vapor pressure were estimated to be 143−172 °C, showing a general dependence on molecular weight. The imidazolylidene complexes were thermally unstable with convincing evidence indicating the unsaturated backbone as a point of weakness. The imidazolinylidene complexes showed excellent thermal stability with comparable results for the formamidinylidenes complexes. The steric parameter of the carbene, %V Bur , was calculated for all complexes characterized by single crystal X-ray diffraction.

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Synthesis of Cu(II) aminoalkoxide complexes and their unusual thermolysis to Cu(0)

Cited by 28 publications

References 32 publications

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

Metal-ligand bond lengths and strengths: are they correlated? A detailed CSD analysis

Study of Monomeric Copper Complexes Supported by N-Heterocyclic and Acyclic Diamino Carbenes

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Synthesis of Cu(II) aminoalkoxide complexes and their unusual thermolysis to Cu(0)

Cited by 28 publications

References 32 publications

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η1:η2-CH2CR2CHCH2)(CO)(PPh3)2andtrans-M(CHCHCMeR2)(CO)(PPh3)2(M = Rh, Ir, R = CH2CH2Ph)

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η1:η2-CH2CR2CHCH2)(CO)(PPh3)2andtrans-M(CHCHCMeR2)(CO)(PPh3)2(M = Rh, Ir, R = CH2CH2Ph)

Metal-ligand bond lengths and strengths: are they correlated? A detailed CSD analysis

Study of Monomeric Copper Complexes Supported by N-Heterocyclic and Acyclic Diamino Carbenes

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C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)