N. Marsich

Substituted phenylcopper(I) compounds

The reaction of CuBr with methyl- and methoxyphenyllithium derivatives and the isolation of the o-tolyl-, m-tolyl-, p-tolyl- and o-anisylcopper are described. Thermal decomposition, hydrolysis and some other reactions are examined. IR and X-ray powder spectra (including phenylcopper) are reported.

Phenylcopper complexes with tertiary phosphines and with triphenylborane

Abstract Reactions of phenylcopper with some representative Lewis bases and acides are described. The complexes (CuPh) 2 PPh 3 , (CuPh) 3 PPh 3 , (CuPh) 2 PBu 3 are reported. The IR absorption frequencies of the PPh 3 complexes in the 1600–700 cm −1 region are assigned and discussed. Tetraphenylboroncopper is obtained by addition of CuPh to BPh 3− . The IR spectrum is assigned and compared with those of other tetraphenylborate compounds.

Complexes of Cu(I) halides with bis(diphenylphosphino)methane and 1,2-bis(diphenylphosphino)ethane

Abstract Cu(I) halide complexes of bis(diphenylphosphino)methane (DPM) and 1,2-bis(diphenylphosphino)ethane (DPE) with Cu(I) X L ratio 2:1, 3:2, 4:3, 1:1 and 2:3 ( X = Cl, Br and often I; L = DPE for 2:3, DPM and DPE for the other complexes) were isolated and characterized by analytical data, conductivity and mole. wt. measurements, i.r. and NMR spectra. Almost always complexes are polymorphic and adducts with solvent of crystallization are frequent.

Organocopper(I) complexes containing nitrogen and phosphorus bidentate ligands

Abstract Some complexes of organocopper(I) compounds with 2,2′-bipyridine, 4,4′- bipyridine, 1,10-phenanthroline, 1,2-bis(diphenylphosphino)ethane and bis(diphenyl- phosphino) methane have been isolated and characterized. The organocopper(I) complexes of 1,2-bis(diphenylphosphino)ethane reacted with dichloroethane to give vinylchloride and the corresponding copper halide complexes. Some new copper(I) chloride complexes of 1,2-bis(diphenylphosphino)ethane are also reported.

Studies on dithio-o-toluate copper(I) complexes with bis(diphenylphosphino)methane. Crystal structures of {di-μ3-dithio-o-toluato-S,S′,S′-bis[μ-bis(diphenylphosphino)methane-μ-dithio-o-toluato-S,S′]} tetracopper(I) and {di[μ-bis(diphenylphosphino)methane]bis(dithio-o-toluato-S,S′)} dicopper(I)

Abstract The structures of [(CuS2CT)2dppm]2 (I) (T = o-tolyl; dppm = bis(diphenylphosphino)methane) and [CuS2CTdppm]2 (II) have been determined by X-ray methods. Crystals of I are monoclinic, space group P21/n, with a = 15.163(4), b = 18.691(5), c = 13.478(4) A, β = 96.81(3)°, Z = 2; crystals of II are orthorhombic. space group Pccn, with a = 23.267(4), b = 13.016(3), c = 20.731(5) A, Z = 4. The structures of I and II have been solved by Patterson and Fourier methods and refined by full-matrix least-squares to R = 0.082 for I and 0.092 for II. The structure of I consists of centrosymmetric tetranuclear complexes in which two pairs of Cu atoms are triply bridged by a dppm ligand and two dithiocarboxylate groups from the dithio-o-toluate ligands. These last behave differently: one of them through a sulphur atom is also bonded to a Cu atom of the other pair so forming a tetranuclear complex. The Cu atoms of each pair show different coordination: Cu(1) displays a distorted trigonal and Cu(2) a distorted trigonal pyramidal geometry. The structure of II consists of dimers, in which each copper atom, doubly bridged by two dppm ligands, completes a distorted trigonal pyramidal coordination through two sulphur atoms from dithio-o-toluate anions acting as chelating ligands. In both compounds the phenyl group of the dithio-o-toluate anions is orthogonal to the corresponding CS2 group. Both complexes give methyldithio-o-toluate in high yields by reaction with methyl iodide.

Stereoselective living polymerization of phenylacetylene promoted by rhodium catalysts with bidentate phosphines

Abstract Polymerization of phenylacetylene to give highly stereoregular cis-transoid polyphenylacetylene is accomplished by use of [Rh(nbd)(OMe)]2 (nbd=norbornadiene) and Ph2P(CH2)xPPh2 (x=2, dppe; x=3, dppp; x=4, dppb). The catalytic system employing the ligand dppb promotes formation of polymer products with low polydispersities. The polymerization is of living nature, as proved by the dependence of polymer molecular weight on conversion and on initial monomer concentration, with molecular weight distributions always maintained within a narrow range. NMR studies of the catalytic system provide information on the rhodium chemistry involved, as well as useful means of comparison to other rhodium–phosphine catalytic systems.

Reaction of carbon dioxide with arylcopper(I) complexes containing tertiary phosphines

Abstract ArCuI compounds (Ar = phenyl, o-, m-, or p-tolyl) do not react with carbon dioxide at appreciable rate, but in the presence of triphenylphosphine in appropriate solvents undergo insertion to give the corresponding carboxylato complexes ArCO2Cu(PPh3)2. In the presence of diphos the carbon dioxide absorption was very slow and mainly gave (ArCO2Cu)2diphos3 complexes. The (diphenylphosphino)methane (DPM) derivatives [ArCO2CuDPM]2 and (ArCO2Cu)2DPM were prepared by other methods for comparison. The X-ray structure of HCO2Cu(PPh3)2 is reported.

On some copper(I) perthiocarboxylates and their reactions with tertiary phosphines. Crystal structure of tetra(p-tolyldithiocarboxylato)tetracopper(I), [CuS2C-p-tolyl]4, and of [bis(triphenylphosphine)(p-tolyldithiocarboxylato)copper(I)] triphenylphosphine sulfide, [CuS2C-p-tolyl(PPh3)2]•PPh3S

Abstract Some copper(I)perthiocarboxylates [CuS 3 CAr] 4 ( I ) ( Ia , ArPh; I b, Ar p -tolyl) were prepared in high yields from the corresponding aldehydes and ammonium polysulfide in basic medium. By reacting them with triphenylphosphine in different ratios, formation of PPh 3 S occurred and the following series of products could be isolated: [(CuS 3 CAr) 2 (CuS 2 - CAr) 2 ]py 2 ( II ); [CuS 2 CAr] 4 ( III ); [(CuS 2 CAr) 4 - (PPh 3 ) 2 ] ( IV ); [CuS 2 CAr(PPh 3 ) 2 ] ( V ). In the case of p -tolyl the complex [CuS 2 CAr(PPh 3 ) 2 ]·PPh 3 S ( VIb ) was also obtained. Some significant IR and NMR ( 13 C, 31 P) data of the above compounds are reported. The crystal structures of compounds IIIb and VIb were established by single crystal X-ray diffraction methods. Crystals of IIIb are triclinic, space group P 1 , with a =13.879(4), b =10.324(3), c =13.479(4) A,α=99.04(2), β=113.31(3), γ= 92.34(2)° and Z =2. Crystals of VIb are also triclinic, space group P 1 , with a =15.833(5), b = 10.999(3), c =15.690(5) A, α=103.12(3), β= 90.88(2), γ=94.05(2)° and Z =2. The structures have been solved by direct and Fourier ( IIIb ) and by Patterson and Fourier ( VIb ) methods and refined by blocked full-matrix least-squares to R =0.059 for IIIb and R =0.051 for VIb . The structure of IIIb consists of discrete units of four copper atoms bound to sulfur atoms from four p -tolyldithiocarboxylate groups acting as tridentate ligands. A sulfur atom of each ligand coordinates to one only copper atom and the other bridges two adjacent metals so that each metal is pseudo-trigonally surrounded by three sulfur atoms. In the structure of VIb monomeric complexes are present in which the metal atom is pseudo-tetrahedrally coordinated by two phosphorous atoms from triphenylphosphine ligands and by two sulfur atoms from one chelating p -tolyldithiocarboxylate group. Triphenylphosphine sulfide molecules are also present in the crystals of VIb . The complex autoxidative reactions of some dithiocarboxylates in pyridine, which cause a partial transformation of the sulfur atoms in coordinated ‘SO 4 ’ groups, were also investigated.

Insertion reactions of carbon disulfide into carbon-copper bonds of aromatic organocopper(I) compounds and of their complexes with triphenylphosphine and bis(diphenylphosphino) ethane

Abstract Aromatic organocopper compounds (phenyl-, m -, p -tolyl-, o -anisyl-copper) react with CS 2 to give unstable copper compounds, except for o =tolycopper, from which polymeric o -TCSSCu ( o -T= o -tolyl) and another derivative, probably [ o -TCSSCU 2 ] n , were obtained. Tritylperoxide is the main by-product in the reaction with phenyl copper. Arylcopper(I) complexes with triphenylphosphine and diphos undergo insertion reaction of CS 2 to form the corresponding dithiocarboxylate complexes ArCSSCu(PPh 3 ) 2 and (ArCSSCu) m - (diphos) n ( m = 1, n = 1; m = 2, n = 3). These afford almost pure ArCSSCH 3 by reaction with CH 3 I. The crystal structure of PhCSSCu(PPh 3 ) 2 has been determined.

A new type of stable organometallic copper complex; properties and structure of the product of the reaction of arylcopper compounds with bis(diphenyl-phosphino)methane

Abstract The complex of empirical formula Cu(Ph2PCH2PPh2) is formed from bis(diphenyl-phosphino)methane and arylcopper compounds, the structure of [Cu(Ph2PCH2PPh2)· 2 3 (PhCH3)] has been determined.