From the reaction of LiNPhPPh2 with Palladium-Nickel- and Cobaltcomplexes, depending on the reaction conditions, different monomeric and dimeric complexes can be isolated. In these compounds the (NPhPPh2)(-)group acts as both a bridging and as a terminal ligand. [Pd(NPhPPh2)(PPh3)](2) (1), [Pd(NPhPPh2)(2) . Li(thf)](2) (2) and [Pd(NPhPPh2)Cl . Li(thf)(3)](2) (3) are formed from the reaction of [PdCl2(PPh3)(2)] or [PdCl2(COD)] with LiNPhPPh2. In contrast to this from the reaction of Pd(Ac)(2) and HNPhPPh2 (in the presence of zinc-dust) or [PtCl2(py)(2)] and LiNPhPPh2 the dimeric complexes [M(NPhPPh2)(HNPhPPh2)](2) (M = Pd: 4; M = Pt: 5) are afforded. The reaction of [MCl2(PR3)(2)] (M = Ni: R = Ph, Pr-i; M = Co: R = Ph) leads to the formation of the monomeric complexes [M{Ph2P(NPh)(2)}(2)] (M = Ni: 6; M = Co: 7) and the dim eric complex [Ni(PPh3){Ph2P(NPh)(2)}](2) (8). When [NiCl2(PPh3)(2)] is reacted with HNPhPPh2 in the presence of zinc-dust [Ni-2(PPh2)(NPhPPh2)(HNPhPPh2)(3)] (9) is formed. The structures of 1-9 were obtained by X-ray single crystal structure analysis. For lattice constants and space groups of 1-9 see "Inhaltsubersicht".
Halogenometallkomplexe und funktionalisierte Amine braucht man für die Synthese imidoverbrückter Übergangsmetallcluster. Auf diesem Weg gelingen auch Synthesen von Imidoclustern elektronenreicher Übergangsmetalle wie [Cu24(μ3‐NPh)8‐(μ4‐NPh)6]4− (die Struktur ist im Bild rechts gezeigt).magnified image
Metal halide complexes and functionalized amines react to form imidobridged transition metal clusters. This method can be used to synthesize imido clusters of electron-rich transition metals such as [Li(thf)4]4-“Cu24(μ3-NPh)8 μ4-NPh)6” 1 (the structure of the anion of 1 is depicted on the right).
AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
The octatelluride [K(15-crown-5)2]2Te8 has been synthesized by the oxydation of a potassium tritelluride solution in dimethylformamide by iron(III) chloride in the presence of 15-crown-5, forming black crystals, which were characterized by an X-ray structure determination. Space group Pca2(1), Z = 4, 4548 observed unique reflections, R = 0.048. Lattice dimensions at -70-degrees-C: a = 1881 (1), b = 2211(2), c = 1530(1) pm. The structure consists of cations [K(15-crown-5)2]+ in which the potassium ions are sandwichlike coordinated by the oxygen atoms of the two disordered crown ether molecules, and of bicyclic Te8(2-) ions. In these anions a Te2+ ion is chelated in a planar fashion by a Te3(2-) and a Te4(2-) unit.
The ionic crown ether complexes [Tl(12-crown-4) 2 ][SbCl 6 ] (1) and [In(12-crown-4) 2 ][SbCl 6 ] 3 .3CH 3 CN (3) have been prepared by reaction of TlCl and InCl 3 , respectively, with SbCl 5 in the presence of 12-crown-4 in acetonitrile solution. The lead complex [Pb(15-crown-5) 2 ][SbCl 6 ] 2 . [SbCl 3 (15-crown-5)] (2) has been obtained from the reaction of Pb(CH 3 ) 2 Cl 2 with SbCl 5 in the presence of 15-crown-5 in acetonitrile solution. 1-3 were characterized by crystal structure determinations
The ionic crown ether complexes [Tl(12-crown-4) 2 ][SbCl 6 ] (1) and [In(12-crown-4) 2 ][SbCl 6 ] 3 .3CH 3 CN (3) have been prepared by reaction of TlCl and InCl 3 , respectively, with SbCl 5 in the presence of 12-crown-4 in acetonitrile solution. The lead complex [Pb(15-crown-5) 2 ][SbCl 6 ] 2 . [SbCl 3 (15-crown-5)] (2) has been obtained from the reaction of Pb(CH 3 ) 2 Cl 2 with SbCl 5 in the presence of 15-crown-5 in acetonitrile solution. 1-3 were characterized by crystal structure determinations
The ionic crown ether complexes [Tl(12-crown-4) 2 ][SbCl 6 ] (1) and [In(12-crown-4)2][SbCl 6 ] 3 ·3 CH 3 CN (3) have been prepared by reaction of T1C1 and InCl 3 , respectively, with SbCl 5 in the presence of 12-crown-4 in acetonitrile solution. The lead complex [Pb(15-crown-5) 2 ][SbCl 6 ] 2 · [SbCl 3 (15-crown-5)] (2) has been obtained from the reaction of Pb(CH 3 ) 2 Cl 2 with SbCl 5 in the presence of 15-crown-5 in acetonitrile solution. 1-3 were characterized by crystal structure determinations. [Tl(12-crown-4) 2 ][SbCl 6 ] (1): Space group C2/c, Z = 4, 2306 observed unique reflections, R = 0.051. Lattice dimensions at -70°C: a = 2360.9(5), b = 1189.6(2), c = 1080.4(3) pm, β = 111.14(2)°. 1 contains cations [Tl(12-crown-4) 2 ] + , in which the Tl+ ion is coordinated sandwichlike by the eight oxygen atoms of the two crown ether molecules. The lone pair at the thallium ion shows steric activity. [Pb(15-crown-5) 2 ][SbCl 6 ] 2 ·[SbCl 3 (15-crown-5)] (2): Space group Pna2(1), Z = 4, 4631 observed unique reflections, R = 0.048. Lattice dimensions at -70°C: a = 2972.5(3), b = 1481.9(5), c = 1305.5(1) pm. 2 consists of [Pb(15-crown-5)2] 2+ ions, in which the lead ion is coordinated sandwich-like by the ten oxygen atoms of the two crown ether molecules without steric activity of the lone pair of Pb 2+ , of SbCl 6 - ions, and of molecules [SbCl 3 (15-crown-5)], which are already known. [In(12-crown-4) 2 ][SbCl 6 ] 3 ·3CH 3 CN (3): Space group P1̅, Z = 2, 5530 observed unique reflections, R = 0.059. Lattice dimensions at -70°C: a = 1041.8(8), b = 1052(1), c = 1543(2) pm, α = 103.62(9)°, β=108.68(8)°, γ = 99.48(8)°. 3 consists of [In(12-crown-4) 2 ] 3+ ions, SbCl 6 - anions, and crystal CH 3 CN molecules. The In 3+ ion is coordinated sandwich-like by the eight oxygen atoms of the two crown ether molecules, which are disordered in two positions
The ionic crown ether complexes [Tl(12-crown-4)2][SbCl6] (1) and [In(12-crown-4)2][SbCl6]3·3 CH3CN (3) have been prepared by reaction of T1C1 and InCl3, respectively, with SbCl5 in the presence of 12-crown-4 in acetonitrile solution. The lead complex [Pb(15-crown-5)2][SbCl6]2· [SbCl3(15-crown-5)] (2) has been obtained from the reaction of Pb(CH3)2Cl2 with SbCl5 in the presence of 15-crown-5 in acetonitrile solution. 1-3 were characterized by crystal structure determinations. [Tl(12-crown-4)2][SbCl6] (1): Space group C2/c, Z = 4, 2306 observed unique reflections, R = 0.051. Lattice dimensions at -70°C: a = 2360.9(5), b = 1189.6(2), c = 1080.4(3) pm, β = 111.14(2)°. 1 contains cations [Tl(12-crown-4)2]+, in which the Tl+ ion is coordinated sandwichlike by the eight oxygen atoms of the two crown ether molecules. The lone pair at the thallium ion shows steric activity. [Pb(15-crown-5)2][SbCl6]2·[SbCl3(15-crown-5)] (2): Space group Pna2(1), Z = 4, 4631 observed unique reflections, R = 0.048. Lattice dimensions at -70°C: a = 2972.5(3), b = 1481.9(5), c = 1305.5(1) pm. 2 consists of [Pb(15-crown-5)2]2+ ions, in which the lead ion is coordinated sandwich-like by the ten oxygen atoms of the two crown ether molecules without steric activity of the lone pair of Pb2+, of SbCl6- ions, and of molecules [SbCl3(15-crown-5)], which are already known. [In(12-crown-4)2][SbCl6]3·3CH3CN (3): Space group P1̅, Z = 2, 5530 observed unique reflections, R = 0.059. Lattice dimensions at -70°C: a = 1041.8(8), b = 1052(1), c = 1543(2) pm, α = 103.62(9)°, β=108.68(8)°, γ = 99.48(8)°. 3 consists of [In(12-crown-4)2]3+ ions, SbCl6- anions, and crystal CH3CN molecules. The In3+ ion is coordinated sandwich-like by the eight oxygen atoms of the two crown ether molecules, which are disordered in two positions
The title compound has been prepared by the reaction of Na2Se4 with mercury acetate in DMF solution in the presence of 15-crown-5, forming dark red crystal needles. [Na(12-crown-4)2]2[Hg(Se4(2] . 1.5 DMF crystallizes in the space group C2/c with eight formula units per unit cell. The structure was determined with 3 824 observed unique reflections, R = 0.085. Lattice dimensions at -70-degrees-C: a = 2884(2), b = 1 407.7(7), c = 2 843(2) pm, beta = 93.93(5)degrees. The structure consists of [Na(12-crown-4)2]+ ions with a sandwichlike coordination of the crown ether molecules, and of [Hg(Se4)2]2-ions, in which the mercury atom is coordinated by two tetraselenido ions in a chelating fashion. The [Hg(Se4)2]2- ions are arranged to infinite chains via Se...Se contacts.
[PbCl(18-crown-6)][SbCl6] has been prepared in low yield besides [Pb(CH3)2(18-crown-6)][SbCl6]2 by the reaction of Pb(CH3)2Cl2 with antimony pentachloride in acetonitrile solution in the presence of 18-crown-6, forming pale-yellow crystals. The other two title compounds are formed as colourless crystals by the reaction of PbCl2 with antimony pentachloride in acetonitrile solutions in the presence of 18-crown-6 and 15-crown-5, respectively. The complexes were characterized by IR spectroscopy and by crystal structure determinations. [PbCl(18-crown-6)][SbCl6]: Space group P2(1)/c, Z = 8, 5003 observed unique reflections, R = 0.046. Lattice dimensions at 80-degrees-C: a = 13 86.9; b = 1 642.7; c = 2 172.1 pm, beta = 92.95-degrees. The lead atom in the cation [PbCl(18-crown-6)]+ is surrounded in an almost hexagonal-planar construction by the six oxygen atoms of the crown ether and an axially oriented Cl atom. [Pb(18-crown-6)(CH3CN)3][SbCl6]2: Space group P1BAR, Z = 2, 6 128 observed unique reflections, R = 0.076. Lattice dimensions at -70-degrees-C: a = 1 228.0; b = 1422.9; c = 1 463.2 pm, alpha = 69.08-degrees; beta = 65.71-degrees; gamma = 64.51-degrees. In the cation [Pb(18-crown-6)(CH3CN)3]2+ the lead atom is coordinated by the six oxygen atoms of the crown ether and by the three nitrogen atoms of the acetonitrile molecules. The structure determination is restricted by disorder. [Pb(15-crown-5)2][SbCl6]2: Space group P6(3)/m, Z = 6, 5 857 observed unique reflections, R = 0.059. Lattice dimensions at -70-degrees-C: a = b = 2 198.5; c = 1 499.4 pm, (alpha = beta = 90-degrees, gamma = 120-degrees. In the cation [Pb(15-crown-5)2]2+ the lead atom is sandwich-like coordinated by the ten oxygen atoms of the two crown ether molecules. The structure determination is restricted by disorder.
