Use of dimethyl sulfide in organocopper chemistry:  x-ray crystal structures of cyclo-tetrakis(.mu.-2-methylphenyl)bis(dimethyl sulfide)tetracopper(I) and of the polymeric copper bromide adduct bromo(dimethyl sulfide)copper(I)

Koten, G. van; Lenders, B.; Smeets, W. J. J.; Sluis, P. van der; Grove, D.M.; Spek, A. L.

doi:10.1021/om00049a046

Cited by 50 publications

(56 citation statements)

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“…Negative (diatropic) NICS values indicate aromaticity, while positive (paratropic) values imply antiaromaticity. Nucleophilic attack of the cyclo-Cu 4 (μ-) 4 species by one and two N 2 nucleophiles does not alter the planarity of the cyclo-Cu 4 (μ-) 4 cluster, yielding the cyclo-Cu 4 (μ 2 -H) 4 ( 1 -N 2 ), 1 and cyclo-Cu 4 (μ 2 -H) 4 ( 1 -N 2 ) 2 , 2, complexes, having C 2v and D 2h symmetry, respectively. Dinitrogen is coordinated to copper(I) centers in an end-on coordination mode ( 1 -N 2 ).…”

Section: Theoretical Methodsmentioning

confidence: 99%

“…Moreover, in complex 2 the distance between the copper atoms, which have not attacked by the nucleophile, is 2.855 Å, indicating weak intermetallic interactions between these two copper atoms as well. On the other hand, nucleophilic attack of the cyclo-Cu 4 (μ-) 4 species by three and four N 2 nucleophiles strongly alters the planarity of the Cu 4 (μ-) 4 core structure, yielding the 3D structures Cu 4 (μ 2 -H) 4 ( 1 -N 2 ) 3 , 3 and Cu 4 (μ 2 -H) 4 ( 1 -N 2 ) 4 , 4, with C 3v and T d symmetry, respectively. It is important to be noticed that in the 3D structures the hydride ligands are triply-bridged facecapping the tetrahedral structure.…”

Section: Theoretical Methodsmentioning

confidence: 99%

“…A variety of structures are obtained upon coordination of one to four CO ligands with the copper(I) metal centers of the parent cyclo-Cu 4 (μ-) 4 cluster. Thus, coordination of one CO ligand yields the cyclo-Cu 4 (μ 2 -H) 4 ( 1 -CO), 5, cluster belonging to C 2v point group.…”

Section: Theoretical Methodsmentioning

confidence: 99%

“…The choice of the copper(I) hydrides was based on the well known tendency of copper(I) centers to cluster together in a variety of organocopper(I) compounds involving even the alkyl groups as bridging ligands, a representative example being the cyclic Cu 4 R 4 tetramer [2][3][4][5][6][7][8][9][10][11]. The cyclic hydrocoppers(I) and some of their substituted derivatives were predicted to be stable species with a perfectly planar configuration, thus expanding the borders of inorganic chemistry into the realm of organic chemistry by building molecules containing bonds that are characterized by a common ring-shaped electron density, more commonly seen in organic molecules, with new properties and chemical reactivity.…”

Section: Introductionmentioning

confidence: 99%

“…Herein we address a number of important issues related to the response of the aromatic cyclo-Cu 4 (μ-) 4 molecule towards successive nucleophilic attack by a series of nucleophiles, Nuc, yielding ligand-stabilized tetranuclear Cu 4 clusters formulated as cyclo-Cu 4 (μ-) 4 Nuc n (n = 1-4; Nuc = N 2 , CO, H 2 O, NH 3 and PH 3 ). The molecular and electronic structures, stabilities and bonding features of these novel ligandstabilized tetranuclear Cu 4 clusters are thoroughly presented, using electronic structure calculation methods at the DFT level of theory.…”

Section: Introductionmentioning

confidence: 99%

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How the Aromatic 4-Membered Hydrido-Bridged Copper Rings Respond to Successive Nucleophilic Attack?

Tsipis¹,

Charistos²

2008

TOMEJ

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Electronic structure calculations (B3LYP/6-311+G**) predict that nucleophilic attack of the aromatic cycloCu 4 (μ-) 4 ring yields ligand-stabilized tetranuclear Cu 4 clusters formulated as cyclo-Cu 4 (μ-) 4 Nuc n (n = 1-4; Nuc = N 2 , CO, H 2 O, NH 3 and PH 3 ). Depending on the number of added nucleophiles, the tetranuclear Cu 4 clusters adopt planar, bent or 3D tetrahedral geometries. These molecules exhibit aromatic character, which is primarily due to 4s and 3d cyclic electron delocalization over the Cu 4 framework (s and d-orbital aromaticity). The aromaticity of the novel ligand stabilized tetranuclear Cu 4 clusters was verified by a number of established criteria of aromaticity. In particular, the nucleusindependent chemical shift, NICS(0) and NICS(1) and their out-of-plane components NICS zz (0), NICS zz (1) and the NICS scan pictures are indicative for the aromaticity of the planar, bent and tetrahedral Cu 4 clusters. The effect of the substituents on the aromatic character of the Cu 4 clusters is also a main concern of the present work. It was found that increasing the number of the attacking nucleophiles increases the diatropic response of the aromatic tetranuclear Cu 4 clusters. Moreover, the aromaticity of the 3D structures (spherical aromaticity) is higher than the aromaticity of the planar and bent structures. The effect of the coordinated nucleophiles, Nuc, on the stability, geometry, electronic structure and bonding mode of the cyclo-Cu 4 (μ-) 4 Nuc n molecules is also thoroughly discussed.

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Section: Theoretical Methodsmentioning

confidence: 99%

Section: Theoretical Methodsmentioning

confidence: 99%

Section: Theoretical Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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How the Aromatic 4-Membered Hydrido-Bridged Copper Rings Respond to Successive Nucleophilic Attack?

Tsipis¹,

Charistos²

2008

TOMEJ

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The Deprotonated Iminophosphoraneo-C6H4PPh2P=NSiMe3 as a Novel Chelating Ligand in Organocopper(I) and -zinc(II) Chemistry

Wingerter

Gornitzka

Bertrand

et al. 1999

Eur. J. Inorg. Chem.

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Lithiation of triphenyl(trimethylsilylimino)phosphorane Ph3P=NSiMe3 with MeLi gives the ortho‐metallated species [Li(o‐C6H4PPh2NSiMe3)]2·Et2O (1), which exhibits all the requirements of an organometallic ligand capable of side‐arm donation. The deprotonated ortho‐phenyl carbon atom gives access to metal–carbon σ bonds in transmetallation reactions, while the Ph2P=NSiMe3 moiety can donate to the same metal center through the imine nitrogen atom. In transmetallation reactions with CuBr, the dimeric organocopper complex [Cu(o‐C6H4PPh2NSiMe3)]2 (2) is obtained, while application of ZnCl2 yields the monomeric zinc complex [Zn(o‐C6H4PPh2NSiMe3)2] (3). Reaction with CuCl2 gives access to the new diiminophosphorane (o‐C6H4PPh2NSiMe3)2 (4) through oxidative coupling at the ortho positions. In all the metal complexes, the Ph2P=NSiMe3 residue acts as a side‐arm donating group through the nitrogen atom. The intermolecular N→Cu donor bond in 2 is as short as copper–amide bonds, while the N→Zn bond lengths in 3 are in the region normally found for donor bonds. Compound 4 is a molecule, possessing two Ph2P=NSiMe3 moieties bridged by a biphenylene group.

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Copper(I) Bromide

Bertz¹,

Fairchild²,

Denissova³

et al. 2004

Encyclopedia of Reagents for Organic Synthesis

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Use of dimethyl sulfide in organocopper chemistry: x-ray crystal structures of cyclo-tetrakis(.mu.-2-methylphenyl)bis(dimethyl sulfide)tetracopper(I) and of the polymeric copper bromide adduct bromo(dimethyl sulfide)copper(I)

Cited by 50 publications

References 1 publication

How the Aromatic 4-Membered Hydrido-Bridged Copper Rings Respond to Successive Nucleophilic Attack?

How the Aromatic 4-Membered Hydrido-Bridged Copper Rings Respond to Successive Nucleophilic Attack?

The Deprotonated Iminophosphoraneo-C6H4PPh2P=NSiMe3 as a Novel Chelating Ligand in Organocopper(I) and -zinc(II) Chemistry

Copper(I) Bromide

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