86024-09-1Relevant articles and documents
(η5-Cyclopentadienyl)- and (η5-Pentamethylcyclopentadienyl)copper Compounds Containing Phosphine, Carbonyl, and η2-Acetylenic Ligands
Macomber, David W.,Rausch, Marvin D.
, p. 5325 - 5329 (1983)
The formation, spectra, and properties of a series of (η5-pentamethylcyclopentadienyl)copper compounds have been investigated.Reactions between lithium pentamethylcyclopentadienide and 4 (R = C6H5, C2H5) produced 5-C5(CH3)5>(PR3)Cu in yields of 43percent and 78percent , respectively.A reaction between lithium pentamethylcyclopentadienide and copper(I) chloride in ethyl ether solution in the presence of carbon monoxide led to 5-C5(CH3)5>(CO)Cu.This carbonyl derivative was both air- and temperature-sensitive and decomposed in solution over 0 deg C to afford copper metal, carbon monoxide, and decamethyl-1,1'-dihydrofulvalene.A reaction between copper(I) chloride and bis(trimethylsilyl)acetylene produced in 76percent yield.Treatment of the latter dimer with lithium pentamethylcyclopentadienide in ether solution afforded .The parent compound was also obtained starting with lithium cyclopentadienide.Both products were air- and temperature-sensitive but could be readily converted into the respective triphenylphosphine derivatives.The complexes and represent the first mixed-sandwich compounds of copper, as predicted by the effective atomic number (EAN) rule.
SYNTHESE UND EIGENSCHAFTEN NEUER KUPFER- UND GOLD-KOMPLEXE DES TYPS C5H5MPR3, C5Me5MPR3 UND R"C2MPR3 (M=Cu, Au) SOWIE DIE KRISTALLSTRUKTUR VON C5H5AuPi-Pr3
Werner, H.,Otto, H.,Ngo-Khac, Tri,Burschka, Ch.
, p. 123 - 136 (1984)
The complexes C5H5CuPR3 (R=Me,i-Pr), C5H5AuPR3 (R=Me,i-Pr), C5Me5CuPR3(R=Me,i-Pr,Ph) and C5Me5AuPR3 (R=i-Pr,Ph) are prepared from n or ClAuPR3 and LiC5H5(TlC5H5) or LiC5Me5, respectively.According to the 1H and 13C NMR spectra, the cyclopentadien
Contrasting structure and bonding of a copper-rich and a zinc-rich intermetalloid cu/zn cluster
Da Silva, Augusto C. H.,Da Silva, Juarez L. F.,F?ssler, Thomas F.,Fischer, Roland A.,Freitag, Kerstin,Gemel, Christian,Kahlal, Samia,Muhr, Maximilian,Saillard, Jean-Yves,Schütz, Max
, (2020)
Reaction of the Cu(I) sources, [Cu5](Mes)5 and [(iDipp)CuOtBu] (Mes = mesityl; iDipp = 1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene) with the Zn(I) complex [Zn2](Cp*)2 leads to a mixture of intermetallic Cu/Zn clusters with a distribution of species that is dependent on the stoichiometric ratio of the reactants, the reaction time, as well as the temperature. Systematic and careful investigation of the product mixtures rendered the isolation of two new clusters possible, i.e., the Zn-rich, red cluster 1, [CuZn10](Cp*)7 = [Cu(ZnZnCp*)3(ZnCp*)4], as well as the Cu-rich, dark-green cluster 2 [Cu10Zn2](Mes)6(Cp*)2. Structure and bonding of these two species was rationalized with the help of density functional theory calculations. Whereas 1 can be viewed as an 18-electron Cu center coordinated to four ZnCp? and three ZnZnCp? one-electron ligands (with some interligand bonding interaction), compound 2 is better to be described as a six-electron superatom cluster. This unusual electron count is associated with a prolate distortion from a spherical superatom structure. This unexpected situation is likely to be associated with the ZnCp? capping units that offer the possibility to strongly bind to the top and the bottom of the cluster in addition to the bridging mesityl ligands stabilizing the Cu core of the cluster.
Mononuclear complexes of copper(I) and silver(I) featuring the metals exclusively bound to carbon. Synthesis and structure of (η 5-pentamethylcyclopentadienyl)[(triphenylphosphonio)- (triphenylphosphoranylidene)methyl]copper(I)
Zybill,Müller
, p. 2489 - 2494 (2008/10/08)
Hexaphenylcarbodiphosphorane, (C6H5)3P=C=P(C6H5) 3, forms monomeric 1:1 adducts [(C6H5)3-P=C=P(C6H5) 3]MCl with CuCl and AgCl. Chloride displacement by the cyclopentadienides M′C5R5 (M′ = Li Na; R = H, CH3) affords the compounds (η5-C5R5)M[(C6H 5)3P=C=P(C6H5)3]. Alternatively, (η5-C5R5)Cu[(C6H 5)3P=C=P(C6H5)3] (R = CH3) is accessible by a stepwise reaction of M′C5R5 with CuCl and (C6H5)3P=C=P(C6H5) 3. The intermediate cationic copper(I) half-sandwich complex [C5R5Cu+] has been trapped with triphenylphosphine. The structure of (η5-C5(CH3)5)Cu[(C 5H5)3P=C=P(C6H5) 3] shows the Cu(I) center to be linearly coordinated by the Cp* ligand and the ylidic C atom of hexaphenylcarbodiphosphorane. The Cu-C(ylide) bond (1.922 (6) A?) is comparable to other 2c-2e bonds. (Crystals of (η5-C5(CH3)5)Cu[(C 6H5)3P=C=P(C6H5) 3] are monoclinic of space group P21/n with a = 11.495 (1) A?, b = 17.147 (2) A?, c = 20.181 (2) A?, β = 101.11 (1)°, V = 3903.2 A?3, and Z = 4. Refinement of 286 parameters on 3499 observables produced Rw = 0.054, w = 1/σ2(Fo).)
