47895-30-7

Upstream product

• 1663-45-2 1,2-bis-(diphenylphosphino)ethane 
• 153479-86-8 {Co2(μ-C2(CH2SCH2CH2)2S)(CO)6(Cu(CH3CN))}(PF6) 
• 127255-91-8 {Cu(1,2-bis(dimethylphosphino)ethane)}{Cu(Co(CO)4)2} 

Relevant academic research and scientific papers

Solid state structural and solution studies on the formation of a flexible cavity for anions by copper(I) and 1,2-bis(diphenylphosphino)ethane

Copper(I) complexes of 1,2-bis(diphenylphosphino)ethane (dppe) with a stoichiometry Cu2(dppe)3(X)2 [X - = CN- (1), SCN- (2), NO3- (3)] are obtained from direct reactions of CuX and dppe. The complexes are structurally and spectroscopically (NMR and IR) characterized. The structure of the [Cu2(dppe)3]2+ dication is similar to the structural motif observed in many other complexes with a chelating dppe and a bridging dppe connecting two copper centers. In complexes 1-3, the anions are confined to the cavity formed by the phosphines which force a monodentate coordination mode despite the predominant bidentate/bridging character of the anions. The coordination angles rather than the thermochemical radii dictate the steric requirement of anions. While the solution behavior of 3, with nitrate, is similar to complexes studied earlier, complexes with pseudohalides exhibit new solution behavior.

Solid-state and solution structural properties of copper(I) compounds with bidentate phosphane ligands

The copper(I) compounds [Cu(dppe)2]X [X = BF4-, I-; dppe = 1,2- bis(diphenylphosphanyl)ethane], [Cu(dppp)2]X [X = BF4-, I-; dppp = 1,3- bis(diphenylphosphanyl)propane], [Cu2(dppe)3I2], and [Cu2(dppe)2I2] have been prepared and their structural properties in solution and in the solid state have been determined. 1H-, 13C-, and 31P-NMR spectra in solution [variable temperature and anion (I-) concentrations] and analyses of solids (mass spectra, elemental analyses, and CPMAS 31P-NMR spectra) are interpreted with equilibria in solution that involve two mono- and two dinuclear species. The structures of [Cu(dppe)2]CIO4, [Cu(dppp)2]BF4, and [Cu2(dppe)3I2] · 2 CHCI3 have been analyzed by X-ray crystallography. In all three structures the copper(I) center adopts a distorted tetrahedral geometry.

Synthesis and Co-ordination Chemistry of Dicobaltcomplexed Thiacycloalkynes

The reactions of bis(2-mercaptoethyl) sulfide or bis(2-mercaptoethyl) ether with CCH2OH)(CO)6> in the presence of HBF4*OEt2 afford (CO)6> (X = S or O) respectively together with dimeric products.The structure of the monomer (CO)6> has been established by X-ray crystallography and comprises a hexacarbonyldicobalt unit transversely bridged via the alkyne functionality of 1,4,7-trithiacycloundec-9-yne which has an exodentate conformation.Proton NMR studies of the bis(2-mercaptoethyl) sulfide derivatives reveal that the SCH2CH2S linkages are predominantly anti in solution.The monomers undergo carbonyl substitution by bis(diphenylphosphino)methane (dppm) to afford (μ-dppm)(CO)4> (X = S or O) which react with to afford products in which the macrocycles face cap Mo(CO)3 fragments.Reaction of (CO)6> with AgBF4 and PPh3 yields (CO)6>BF4 for which an X-ray crystallographic study revealed that the Ag(PPh3)(1+) fragment is co-ordinated by all three sulfur atoms of the ring which adopts an endodentate conformation.Reaction of (CO)6> with PF6 affords (CO)6>PF6 containing a labile acetonitrile ligand which undergoes substitution by phosphines.The dimeric compound Co2(CO)6> produces a 1:1 adduct when treated with AgBF4.X-Ray crystallography reveals that the silver ion is co-ordinated by four of the six available thioether groups.

Crystal structure and reactivity of [Cu(dmpe)2][Cu(Co(CO)4)2] (dmpe = 1,2-bis(dimethylphosphino)ethane): Staggered and eclipsed conformations of [(CO)4CoCuCo(CO)4]- anions

The reaction of NaCo(CO)4 with 1,2-bis(dimethylphosphino)ethane (dmpe) and CuCl in dichloromethane solution gave pale yellow, air-sensitive [Cu(dmpe)2][Cu(Co(CO)4)2], which has been characterized by X-ray crystallography at room temperature. The crystals are monoclinic, space group C2/c, with unit cell dimensions a = 18.437 (5) ?, b = 9.880 (2) ?, c = 38.109 (9) ?, β = 102.07 (2)°, V = 6788 (3) ?3, Z = 8, and RwF = 6.02%. The anions [(CO)4CoCuCo(CO)4]- are monomers with staggered and eclipsed forms existing simultaneously in the unit cell. The staggered form adopts a linear conformation around copper, whereas in the eclipsed form the Co-Cu-Co bond angle is slightly less than 180°. Reaction of 2 equiv of the ligand dppe (1,2-bis(diphenylphosphino)ethane) with [Cu(Co(CO)4)2]- at -78°C instantly affords the Co(CO)4- anion and Cu(dppe)2+, indicative of a highly labile Cu-Co bond.

Electroanalytical and Spectrophotometric Investigations on the Metal(II)-1,2-Bis(diphenylphosphino)ethane-Acetylacetonate System (M = Ni, Pd, or Cu) in Acetonitrile

The soft-hard mixed-ligand complexes + have been characterized by a combination of electroanalytical and spectrophotometric measurements.These species can easily be synthesized in acetonitrile both by a ligand conproportionation reaction upon starting from the corresponding acetylacetonate and diphosphine homoleptic species and from stoicheiometric amounts of 2+ and acac-.Upon reaction of equimolar amounts of and dppe, the same synthesis can be achieved in the case of M = Pd, while for M = Ni the ligand-exchange reaction is followed by the reduction of nickel(II) to nickel(I) and nickel(0) occuring at the expense of the displaced acac-.The mixed-ligand complex cannot ne obtained for Cu in that copper(II) is reduced to copper(I) when dppe is present.In this low oxidation state copper is unable to co-ordinate acac- and appears to be stable as + or +.

Copper(I) complexes with bidentate tertiary phosphine ligands: Solution chemistry and antitumor activity

Copper may play an important role in the antitumor activity of diphosphines. The tetrahedral bischelated copper(I) complexes [Cu(dppey)2]Cl and [Cu(dppp)2]Cl, where dppey is Ph2PCH=CHPPh2 and dppp is Ph2P(CH2)3PPh2, were synthesized and characterized. The bridged dicopper(I) complex (CuCl)2(dppe)3, where dppe is Ph2P(CH2)2PPh2, underwent dissociative equilibria in CDCl3 and CD2Cl2 solutions, as determined by temperature-dependent 1H and 31P NMR studies. One of the products was [Cu(dppe)2]+, the proportion of which increased on adding excess dppe. The complex was also a product from the reaction of Cu2+ with excess dppe in DMA. The complexes [Cu(P-P)2]Cl, where P-P is dppey or dppp, and (CuCl)2(dppe)3 were all active against P388 leukemia, M5076 reticulum cell sarcoma, and B16 melanoma. [Cu(eppe)2]Cl, where eppe is Et2P(CH2)2PPh2, was active only against P388 leukemia. The activities were comparable to those of the analogous Au(I) complexes, and complexes were more potent than the free ligands.