Synthesis,Spectroscopy, and Structures of Mono‐ and Dinuclear Copper(I) Halide Complexes with 1,3‐Imidazolidine‐2‐thiones

Copper(I) halides with triphenyl phosphine and imidaozlidine‐2‐thiones (L ‐NMe, L ‐NEt, and L ‐NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed‐ligand complexes: mononuclear, namely, [CuCl(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 1 ), [CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 2 ), [CuBr(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 5 ), [CuI(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 6 ), [CuCl(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 7 ), and [CuBr(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 8 ), and dinuclear, [Cu₂(κ¹‐I)₂(μ‐S‐L ‐NMe)₂(PPh₃)₂] ( 3 ) and [Cu₂(μ‐Cl)₂(κ¹‐S‐L ‐NEt)₂(PPh₃)₂] ( 4 ). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X‐ray crystallography. Complexes 2 – 4 , 7 , and 8 each formed crystals in the triclinic system with P$\bar{1}$ space group, whereas complexes 1 , 5 , and 6 crystallized in the monoclinic crystal system with space groups P2₁/c, C2/c, and P2₁/n, respectively. Complex 2 has shown two independent molecules, [(CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] and [CuBr(PPh₃)₂] in the unit cell. For X = Cl, the thio‐ligand bonded to metal as terminal in complex 4 , whereas for X = I it is sulfur‐bridged in complex 3 .     

Die Kristallstrukturen von PPh4[MCl5(NCMe)] · MeCN (M = Ti,Zr), zwei Modifikationen von PPh4[TiCl5(NCMe)] und von cis‐TiCl4(NCMe)2 · MeCN

The Crystal Structures of PPh₄[MCl₅(NCMe)] · MeCN (M = Ti, Zr), two Modifications of PPh₄[TiCl₅(NCMe)] and of cis ‐TiCl₄(NCMe)₂ · MeCN The title compounds were obtained by reactions of TiCl₄ or ZrCl₄, respectively, with PPh₄Cl and acetonitrile in the presence of S₂Cl₂. PPh₄[TiCl₅(NCMe)] · MeCN is unstable and emanates the incorporated acetonitrile. PPh₄[TiCl₅(NCMe)] forms the two modifications aP114 and mP228, the latter being more stable. The crystal structures were determined by X‐ray diffraction. Triclinic PPh₄[TiCl₅(NCMe)]‐(aP114) crystallizes in a distorted variety at the tetragonal AsPh₄[RuNCl₄] type, i. e. with PPh₄⁺ ions that are piled to columns in the c direction; the [TiCl₅(NCMe)]^– ions are tilted vs. this direction and thus cause the symmetry reduction from P4/n to P1. PPh₄[TiCl₅(NCMe)] · MeCN and PPh₄[ZrCl₅(NCMe)] · MeCN also have the same packing principle as in AsPh₄[RuNCl₄] with a symmetry reduction from P4/n to P112₁/n and a doubled c axis. Instead, PPh₄[TiCl₅(NCMe)]‐(mP228) has a packing with (PPh₄⁺)₂ pairs. Orthorhombic TiCl₄(NCMe)₂ · MeCN contains molecules having two acetonitrile ligands attached to the Ti atom in a cis configuration.     

Nickel(II) Complexes of 1‐Alkyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.13,7]decane – Synthesis and Solid‐State Structures

Complexes [NiI₃(mpta)₂]I ( 1 ) and [NiI₃(ppta)₂]I ( 2 ) have been synthesized by reaction of nickel(II) halide salts with ‐1‐methyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.1^3,7]decane iodide (mpta⁺I^?) and 1‐(n‐propyl)‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.1^3,7]decane bromide (ppta⁺Br^?) respectively. The crystal structures of compounds 1 and 2 are described and are similar, with both compounds crystallizing in monoclinic space groups. The geometry about both nickel atoms is that of a trigonal bipyramid with the cationic phosphine ligands found in the axial positions and the iodide ligands arranged in the equatorial plane.     

Complexes of N‐Thiophosphorylthiourea α‐NaphthylNHC(S)NHP(S)(OiPr)2 (HL) with Copper(I). Crystal Structures of HL and Cu(PPh3)2L

Reaction of the potassium salt of N‐thiophosphorylated thiourea α‐naphthylNHC(S)NHP(S)(OiPr)₂ ( HL ) with Cu(PPh₃)₃I in aqueous EtOH/CH₂Cl₂ leads to the mononuclear complex [Cu(PPh₃)₂L–S,S′]. By using copper(I) iodide instead ofCu(PPh₃)₃I, the polynuclear complex [Cu_n(L–S,S′)_n] was obtained. The structures of these compounds were investigated by elemental analysis, ¹H and ³¹P{¹H} NMR and IR spectroscopy. The crystal structures of HL and Cu(PPh₃)₂L were determined by single‐crystal X‐ray diffraction.     

Ring‐to‐Cage Structural Conversion via Template Effect in a Gold(I) Metallosupramolecular System

A unique example of a ring‐to‐cage structural conversion in a multinuclear gold(I) coordination system with d ‐penicillamine (d ‐H₂pen) is reported. The reaction of [Au₂Cl₂(dppe)] (dppe=1,2‐bis(diphenylphosphino)ethane) with d ‐H₂pen in a 1:1 ratio gave [Au₄(dppe)₂(d ‐pen)₂] ([ 1 ]), in which two [Au₂(dppe)]²⁺ units are linked by two d ‐pen S atoms in a cyclic form so as to have two bidentate‐N,O coordination arms. The subsequent reaction of [ 1 ] with Cu(OTf)₂ afforded [Au₄Cu(dppe)₂(d ‐pen)₂]²⁺ ([ 2 ]²⁺), in which a Cu^II ion is chelated by the two coordination arms in [ 1 ] to form an Au^I₄Cu^II bicyclic metallocage. A similar reaction using Cu(NO₃)₂ was accompanied by the ring expansion of [ 1 ] to [Au₈(dppe)₄(d ‐pen)₄], leading to the production of [Au₈Cu₂(dppe)₄(d ‐pen)₄]⁴⁺ ([ 3 ]⁴⁺). In [ 3 ]⁴⁺, two Cu^II ions are each chelated by the two coordination arms to form an Au^I₈Cu^II₂ tricyclic metallocage, accommodating a nitrate ion. The use of Ni(NO₃)₂ or Ni(OAc)₂ instead of Cu(NO₃)₂ commonly gave a tricyclic metallocage of [Au₈Ni₂(dppe)₄(d ‐pen)₄]⁴⁺ ([ 4 ]⁴⁺), but a water molecule was accommodated inside the Au^I₈Ni^II₂ metallocage.     

An Extremely Porous Hydrogen‐Bonded Framework Composed of d‐Penicillaminato CoIII2AuI3 Complex Anions and Aqua Cobalt(II) Cations: Formation and Stepwise Structural Transformation

A unique example of a hydrogen‐bonded ionic solid with a porosity of 80 %, [Co(H₂O)₆]₃[Co₂Au₃(d ‐pen‐N,S)₆]₂ ( 1 ; d ‐H₂pen=d ‐penicillamine), composed of [Co(H₂O)₆]²⁺ cations and [Co₂Au₃(d ‐pen‐N,S)₆]^3? anions, is reported. Solid 1 was kinetically produced and was then transformed stepwise into two more thermodynamically stable solids with lower porosities, [Co(H₂O)₄][Co(H₂O)₆]₂[Co₂Au₃(d ‐pen‐N,S)₆]₂ ( 2 ) and [Co(H₂O)₄]₃[Co₂Au₃(d ‐pen‐N,S)₆]₂ ( 3 ), through the coordination of the free carboxylate groups in [Co₂Au₃(d ‐pen‐N,S)₆]^3? to Co^II centers. Solids 1 – 3 were structurally characterized, and the selective adsorption of small molecules into their pores was investigated.     

Assembling Quasi‐enantiomeric Octahedral Complexes of Different Metals via Quasi‐racemate Crystallization

Aiming at a general methodology for binary co‐assembly of complexes of different metals through quasiracemate crystallization, the hexadentate ligand 1 comprised of the chiral bipyrrolidine core and two bipyridine peripheral arms is introduced. Ligand 1 was found to bind in a fully diastereoselective and uniform mode around Zn^II, Fe^II and Cd^II giving coordinatively inert octahedral “chiral‐at‐metal” complexes with the Δ₄Λ₂/Λ₄Δ₂ wrapping mode. Equimolar mixtures of quasienantiomeric pairs of these complexes exhibited a clear tendency to pack as quasiracemates as was revealed from the crystallographic structures of [(R,R)‐ 1 ‐Zn](PF₆)₂/[(S,S)‐ 1 ‐Fe](PF₆)₂ and [(R,R)‐ 1 ‐Zn](PF₆)₂/[(S,S)‐ 1 ‐Cd](PF₆)₂, in an isomorphous fashion to that of the racemic compound [rac‐ 1 ‐Zn](PF₆)₂ in space group C2/c.     

Nickel(II) N‐Benzyl‐N‐methyldithiocarbamato Complexes as Precursors for the Preparation of Graphite Oxidation Accelerators

The nickel(II) N‐benzyl‐N‐methyldithiocarbamato (BzMedtc) complexes [Ni(BzMedtc)(PPh₃)Cl] ( 1 ), [Ni(BzMedtc)(PPh₃)Br] ( 2 ), [Ni(BzMedtc)(PPh₃)I] ( 3 ), and [Ni(BzMedtc)(PPh₃)(NCS)] ( 4 ) were synthesized using the reaction of [Ni(BzMedtc)₂] and [NiX₂(PPh₃)₂] (X = Cl, Br, I and NCS). Subsequently, complex 1 was used for the preparation of [Ni(BzMedtc)(PPh₃)₂]ClO₄ ( 5 ), [Ni(BzMedtc)(PPh₃)₂]BPh₄ ( 6 ), and [Ni(BzMedtc)(PPh₃)₂]PF₆ ( 7 ). The obtained complexes 1 – 7 were characterized by elemental analysis, thermal analysis and spectroscopic methods (IR, UV/Vis, ³¹P{¹H} NMR). The results of the magnetochemical and molar conductivity measurements proved the complexes as diamagnetic non‐electrolytes ( 1 – 4 ) or 1:1 electrolytes ( 5 – 7 ). The molecular structures of 4 and 5· H₂O were determined by a single‐crystal X‐ray analysis. In all cases, the Ni^II atom is tetracoordinated in a distorted square‐planar arrangement with the S₂PX, and S₂P₂ donor set, respectively. The catalytic influence of selected complexes 1 , 3 , 5 , and 6 on graphite oxidation was studied. The results clearly indicated that the presence of the products of thermal degradation processes of the mentioned complexes has impact on the course of graphite oxidation. A decrease in the oxidation start temperatures by about 60–100 °C was observed in the cases of all the tested complexes in comparison with pure graphite.     

Synthesis,Structures, and Reactivities of Pincer‐Type Ruthenium Complexes Bearing Two Proton‐Responsive Pyrazole Arms

A new metal–ligand bifunctional, pincer‐type ruthenium complex [RuCl( L1‐H2 )(PPh₃)₂]Cl ( 1 ; L1‐H2 =2,6‐bis(5‐tert‐butyl‐1H‐pyrazol‐3‐yl)pyridine) featuring two proton‐delivering pyrazole arms has been synthesized. Complex 1 , derived from [RuCl₂(PPh₃)₃] with L1‐H2 , underwent reversible deprotonation with potassium carbonate to afford the pyrazolato–pyrazole complex [RuCl(L1‐H)(PPh₃)₂] ( 2 ). Further deprotonation of 1 and 2 with potassium hexamethyldisilazide in methanol resulted in the formation of the bis(pyrazolato) complex [Ru(L1)(MeOH)(PPh₃)₂] ( 3 ). Complex 3 smoothly reacted with dioxygen and dinitrogen to give the side‐on peroxo complex [Ru(L1)(O₂)(PPh₃)₂] ( 4 ) and end‐on dinitrogen complex [Ru(L1)(N₂)(PPh₃)₂] ( 5 ), respectively. On the other hand, the reaction of [RuCl₂(PPh₃)₃] with less hindered 2,6‐di(1H‐pyrazol‐3‐yl)pyridine ( L3‐H2 ) led to the formation of the dinuclear complex [{RuCl₂(PPh₃)₂}₂(μ₂‐ L3‐H2 )₂] ( 6 ), in which the pyrazole‐based ligand adopted a tautomeric form different from L1‐H2 in 1 and the central pyridine remained uncoordinated. The detailed structures of 1 , 2 , 3 , 3.MeOH , 4 , 5 , 6 were determined by X‐ray crystallography.     

Coordination Behavior of a D‐Penicillaminato Aurate(I) Metalloligand Toward Coblat(III) Centers

Treatment of (NH₄)[Au(D‐Hpen‐S)₂](D‐H₂pen = D‐penicillamine) with CoCl₂·6H₂O in an acetate buffer solution, followed by air oxidation, gave neutral Au^ICo^III and anionic Au^I₃Co^III₂ polynuclear complexes, [Au₃Co₃(D‐pen‐N,O,S)₆]([ 1 ]) and [Au₃Co₂(D‐pen‐N,S)₆]^3? ([ 2 ]^3?), which were separated by anion‐exchange column chromatography. Complexes [ 1 ] and [ 2 ]^3? each formed a single isomer, and their structures were determined by single‐crystal X‐ray crystallography. In [ 1 ], each of three [Au(D‐pen‐S)₂]^3?metalloligands coordinates to two Co^III ions in a bis‐tridentate‐N,O,S mode to form a cyclic Au^I₃Co^III₃ hexanuclear structure, in which three [Co(D‐pen‐N,O,S)₂]^? octahedral units and six bridging S atoms adopt trans(O) geometrical and R chiral configurations, respectively. In [ 2 ]^3?, each of three [Au(D‐pen‐S)₂]^3? metalloligands coordinates to two Co^III ions in a bis‐bidentate‐N,S mode to form a Au^I₃Co^III₂ pentanuclear structure, in which two [Co(D‐pen‐N,S)₃]^3? units and six bridging S atoms adopt ∧ and R chiral configurations, respectively.     

A synchrotron radiation study of the one‐dimensional complex of sodium with (1S)‐N‐carboxylato‐1‐(9‐deazaadenin‐9‐yl)‐1,4‐dideoxy‐1,4‐imino‐d‐ribitol,a member of the 'immucillin' family

The sodium salt of [immucillin‐A–CO₂H]⁻ (Imm‐A), namely catena‐poly[[[triaquadisodium(I)](μ‐aqua)[μ‐(1S)‐N‐carboxylato‐1‐(9‐deazaadenin‐9‐yl)‐1,4‐dideoxy‐1,4‐imino‐d ‐ribitol][triaquadisodium(I)][μ‐(1S)‐N‐carboxylato‐1‐(9‐deazaadenin‐9‐yl)‐1,4‐dideoxy‐1,4‐imino‐d ‐ribitol]] tetrahydrate], {[Na₂(C₁₂H₁₃N₄O₆)₂(H₂O)₇]·4H₂O}_n, (I), forms a polymeric chain via Na⁺—O interactions involving the carboxylate and keto O atoms of two independent Imm‐A molecules. Extensive N,O—H...O hydrogen bonding utilizing all water H atoms, including four waters of crystallization, provides crystal packing. The structural definition of this novel compound was made possible through the use of synchrotron radiation utilizing a minute fragment (volume ∼2.4 × 10⁻⁵ mm⁻³) on a beamline optimized for protein data collection. A summary of intra‐ring conformations for immucillin structures indicates considerable flexibility while retaining similar intra‐ring orientations.     

Synthesis,Characterization, and X‐ray Structures of Ru3(CO)9(dotpm)(L) Complexes [L = PPh3, P(C6H4Cl‐p)3, and PPh2(C6H4Br‐p)]

The reaction of Ru₃(CO)₁₀(dotpm) ( 1 ) [dotpm = (bis(di‐ortho‐tolylphosphanyl)methane)] and one equivalent of L [L = PPh₃, P(C₆H₄Cl‐p)₃ and PPh₂(C₆H₄Br‐p)] in refluxing n‐hexane afforded a series of derivatives [Ru₃(CO)₉(dotpm)L] ( 2 – 4 ), respectively, in ca. 67–70 % yield. Complexes 2 – 4 were characterized by elemental analysis (CHN), IR, ¹H NMR, ¹³C{¹H} NMR and ³¹P{¹H} NMR spectroscopy. The molecular structures of 2 , 3 , and 4 were established by single‐crystal X‐ray diffraction. The bidentate dotpm and monodentate phosphine ligands occupy equatorial positions with respect to the Ru triangle. The effect of substitution resulted in significant differences in the Ru–Ru and Ru–P bond lengths.     

Co‐crystals of 3‐deoxy‐3‐fluoro‐α‐d‐glucopyranose and 3‐deoxy‐3‐fluoro‐β‐d‐glucopyranose

3‐Deoxy‐3‐fluoro‐d ‐glucopyranose crystallizes from acetone to give a unit cell containing two crystallographically independent molecules. One of these molecules (at site A) is structurally homogeneous and corresponds to 3‐deoxy‐3‐fluoro‐β‐d ‐glucopyranose, C₆H₁₁FO₅, (I). The second molecule (at site B) is structurally heterogeneous and corresponds to a mixture of (I) and 3‐deoxy‐3‐fluoro‐α‐d ‐glucopyranose, (II); treatment of the diffraction data using partial‐occupancy oxygen at the anomeric center gave a high‐quality packing model with an occupancy ratio of 0.84:0.16 for (II):(I) at site B. The mixture of α‐ and β‐anomers at site B appears to be accommodated in the lattice because hydrogen‐bonding partners are present to hydrogen bond to the anomeric OH group in either an axial or equatorial orientation. Cremer–Pople analysis of (I) and (II) shows the pyranosyl ring of (II) to be slightly more distorted than that of (I) [θ_(I) = 3.85 (15)° and θ_(II) = 6.35 (16)°], but the general direction of distortion is similar in both structures [ϕ_(I) = 67 (2)° (B_C1,C4) and ϕ_(II) = 26.0 (15)° (^C3TB_C1); B = boat conformation and TB = twist‐boat conformation]. The exocyclic hydroxymethyl (–CH₂OH) conformation is gg (gauche–gauche) (H5 anti to O6) in both (I) and (II). Structural comparisons of (I) and (II) to related unsubstituted, deoxy and fluorine‐substituted monosaccharides show that the gluco ring can assume a wide range of distorted chair structures in the crystalline state depending on ring substitution patterns.     

Zur Reaktivität von alkylthioverbrückten 44‐CVE‐triangularen Platinclustern: Umsetzungen mit bidentaten Phosphanliganden

On the Reactivity of Alkylthio Bridged 44 CVE Triangular Platinum Clusters: Reactions with Bidentate Phosphine Ligands The 44 cve (cluster valence electrons) triangular platinum clusters [{Pt(PR₃)}₃(μ‐SMe)₃]Cl (PR₃ = PPh₃, 2a ; P(4‐FC₆H₄)₃, 2b ; P(n‐Bu)₃, 2c ) were found to react with PPh₂CH₂PPh₂ (dppm) in a degradation reaction yielding dinuclear platinum(I) complexes [{Pt(PR₃)}₂(μ‐SMe)(μ‐dppm)]Cl (PR₃ = PPh₃, 3a ; P(4‐FC₆H₄)₃, 3b ; P(n‐Bu)₃; 3e ) and the platinum(II) complex [Pt(SMe)₂(dppm)] ( 4 ), whereas the addition of PPh₂CH₂CH₂PPh₂ (dppe) to cluster 2a afforded a mixture of degradation products, among others the complexes [Pt(dppe)₂] and [Pt(dppe)₂]Cl₂. On the other hand, the treatment of cluster 2a with PPh₂CH₂CH₂CH₂PPh₂ (dppp) ended up in the formation of the cationic complex [{Pt(dppp)}₂(μ‐SMe)₂]Cl₂ ( 5 ). Furthermore, the terminal PPh₃ ligands in complex 3a proved to be subject to substitution by the stronger donating monodentate phosphine ligands PMePh₂ and PMe₂Ph yielding the analogous complexes [{Pt(PR₃)}₂(μ‐SMe)(μ‐dppm)]Cl (PR₃ = PMePh₂, 3c ; PMe₂Ph, 3d ). NMR investigations on complexes 3 showed an inverse correlation of Tolmans electronic parameter ν with the coupling constants ¹J(Pt,P) and ¹J(Pt,Pt). All compounds were fully characterized by means of NMR and IR spectroscopy. X‐ray diffraction analyses were performed for the complexes [{Pt{P(4‐FC₆H₄)₃}}₂(μ‐SMe)(μ‐dppm)]Cl ( 3b ), [Pt(SMe)₂(dppm)] ( 4 ), and [{Pt(dppp)}₂(μ‐SMe)₂]Cl₂ ( 5 ).     

pH‐Controlled Multiple Chiral Inversion That Induces Molecular Dimerization in a Gold(I)–Cobalt(III) Coordination System with L‐Cysteinate

Herein, a unique coordination system that exhibits multiple chiral inversions and molecular dimerization in response to a subtle pH change is reported. Treatment of (Δ)₂‐H₃[Au₃Co₂(L ‐cys)₆] (H₃[ 1 a ]) with [Co₃(aet)₆](NO₃)₃ (aet=2‐aminoethanethiolate) in water at pH 7 gave a 1:1 complex salt of [Co₃(aet)₆]³⁺ and [ 1 a ]^3?, retaining the Au^I₃Co^III₂ structure and chiral configurations of [ 1 a ]^3?. Similar treatment at pH 9 led to not only the inversion of all of the chiral Co^III and S centers but also the dimerization of [ 1 a ]^3?, giving a 2:1 complex salt of [Co₃(aet)₆]³⁺ and (Λ)₄(R)₁₂‐[Au₆Co₄(L ‐cys)₁₂]^6? ([ 2 ]^6?). When dissociated from [Co₃(aet)₆]³⁺ in solution, [ 2 ]^6? was converted to (Λ)₂(R)₆‐[Au₃Co₂(L ‐cys)₆]^3? ([ 1 b ]^3?) with retention of the chiral configurations.     

Synthesis of 2‐aminomethylpiperidine ruthenium(II) phosphine complexes and their applications in transfer hydrogenation of aryl ketones

The complex trans,cis‐[RuCl₂(PPh₃)₂(ampi)] (2) was prepared by reaction of RuCl₂(PPh₃)₃ with 2‐aminomethylpiperidine(ampi) (1). [RuCl₂(PPh₂(CH₂)_nPPh₂)(ampi) (n = 3, 4, 5)] (3–5) were synthesized by displacement of two PPh₃ with chelating phosphine ligands. All complexes (2–5) were characterized by ¹ H, ¹³C, ³¹P NMR, IR and UV‐visible spectroscopy and elemental analysis. They were found to be efficient catalysts for transfer hydrogen reactions. Copyright © 2012 John Wiley & Sons, Ltd.     

Chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ2P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate

The aminophosphane ligand 1‐amino‐2‐(diphenylphosphanyl)ethane [Ph₂P(CH₂)₂NH₂] reacts with dichloridotris(triphenylphosphane)ruthenium(II), [RuCl₂(PPh₃)₃], to form chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ²P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate, [RuCl(C₁₈H₁₅P)(C₁₄H₁₆NP)₂]Cl·C₇H₈ or [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]Cl·C₇H₈. The asymmetric unit of the monoclinic unit cell contains two molecules of the Ru^II cation, two chloride anions and two toluene molecules. The Ru^II cation is octahedrally coordinated by two chelating Ph₂P(CH₂)₂NH₂ ligands, a triphenylphosphane (PPh₃) ligand and a chloride ligand. The three P atoms are meridionally coordinated, with the Ph₂P– groups from the ligands being trans. The two –NH₂ groups are cis, as are the chloride and PPh₃ ligands. This chiral stereochemistry of the [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]⁺ cation is unique in ruthenium–aminophosphane chemistry.     

[Au(C6F5)3(PPh2H)]: A Precursor for the Synthesis of Gold(III) Phosphide Complexes

The covalent radius of Au ^I is about 0.07 Å smaller than that of Ag^I. This was determined from the crystal structures of the isostructural complexes [N(PPh₃)][{Au(C₆F₅)₃(μ-PPh₂)}₂M] (M=Au (structure shown in the picture), Ag). These mixed Au^III–M phosphides were synthesized from [Au(C₆F₅)₃(PPh₂H)], the first gold complex to contain a secondary phosphane.     

Poly[[diaqua‐μ‐4,4′‐bipyridine‐dinitratodi‐μ‐l‐tyrosinato‐dicopper(II)]: a chiral two‐dimensional coordination polymer

The title compound, [Cu₂(C₉H₁₀NO₃)₂(NO₃)₂(C₁₀H₈N₂)(H₂O)₂]_n, contains Cu^II atoms and l ‐tyrosinate (l ‐tyr) and 4,4′‐bipyridine (4,4′‐bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two l ‐tyr ligands, one N atom from a 4,4′‐bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4′‐bipy ligands, forming an undulated chiral two‐dimensional sheet. O—H...O and N—H...O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4′‐bipy ligands by considering the ratios of the metal ion and organic components.     

Triphenylphosphan-Nickel(0)-Komplexe mit Isocyanid-Liganden — [(RNC)nNi(PPh3)4–n] (n = 1–3)

Triphenylphosphane Nickel(0) Complexes with Isocyanide Ligands — [(RNC)_nNi(PPh₃)_4–n] (n = 1–3) Synthesis and properties of the isocyanide triphenylphosphane nickel(0) complexes [(RNC)Ni(PPh₃)₃], [(RNC)₂Ni(PPh₃)₂] and [(RNC)₃Ni(PPh₃)] (R = ^tBu, Cy, PhCH₂, p-TosCH₂) are described. I.r. and ³¹P n.m.r. spectra were recorded and the X-ray crystal structure of [(PhCH₂NC)₂Ni(PPh₃)₂] was determined.