Synthesis and Spectroscopic Characterization of New Lead(II) Thiosaccharinates. Molecular Structure of Bis(thiosaccharinato)tetrakis(pyridine)dilead(II) and Thiosaccharinato‐bis(1,10‐phenantroline)lead(II) Thiosaccharinate

Four new lead(II) thiosaccharinate complexes: [Pb(tsac)₂H₂O] (1) (tsac: thiosaccharinate anion), [Pb₂(tsac)₄(py)₄] (2) (py: pyridine), [Pb(tsac)(o‐phen)₂](tsac)·CH₃CN (3) (o‐phen: 1,10‐phenantroline), and [Pb(tsac)₂(bipy)] (4) (bipy: 2,2′‐bipyridine) were prepared. The infrared and electronic spectra as well as the thermal analysis of all the compounds were recorded and discussed. The thiosaccharinate anion acts in three different coordination forms, one of then reported for the first time. The crystal structures of complexes 2 and 3 have been determined by single crystal X‐ray diffractometry. In complex 2 , two monomeric moieties are joined together forming a symmetric bis‐μ‐sulphur bridged dimer by interaction of two lead(II) atoms through the exocyclic sulphur atoms of two thiosaccharinate ligands. The seven‐fold coordination sphere of each lead atom is completed by two pyridine nitrogen atoms and by another sulfur and two nitrogen atoms of the thiosaccharinate anions. In complex 3 , the lead(II) atom is coordinated by four nitrogen atoms of two 1,10‐phenantroline molecules and by the sulfur and nitrogen atoms of one thiosaccharinate ion. The second anion has an electrostatic interaction with the nucleus.     

Synthesis and Structural Analysis of New Palladium(II) Thiosaccharinates with Triphenylphosphane or Diphosphanes

A series of palladium(II) thiosaccharinates with triphenylphosphane (PPh₃), bis(diphenylphosphanyl)methane (dppm), and bis(diphenylphosphanyl)ethane (dppe) have been prepared and characterized. From mixtures of thiosaccharin, Htsac, and palladium(II) acetylacetonate, Pd(acac)₂, the palladium(II) thiosaccharinate, Pd(tsac)₂ (tsac: thiosaccharinate anion) ( 1 ) was prepared. The reaction of 1 with PPh₃, dppm, and dppe leads to the mononuclear species Pd(tsac)₂(PPh₃)₂ · MeCN ( 2 ), [Pd(tsac)₂(dppm)] ( 3 ), Pd(tsac)₂(dppm)₂ ( 4 ), and [Pd(tsac)₂(dppe)] · MeCN ( 5 ). Compounds 2 , 4 , and 5 have been prepared also by the reaction of Pd(acac)₂ with the corresponding phosphane and Htsac. All the new complexes have been characterized by chemical analysis, UV/Vis, IR, and Raman spectroscopy. Some of them have been also characterized by NMR spectroscopy. The crystalline structures of complexes 3 , and 5 have been studied by X‐ray diffraction techniques. Complex 3 crystallizes in the monoclinic space group P2₁/n with a = 16.3537(2), b = 13.3981(3), c = 35.2277(7) Å, β = 91.284(1)°, and Z = 8 molecules per unit cell, and complex 5 in P2₁/n with a = 10.6445(8), b = 26.412(3), c = 15.781(2) Å, β = 107.996(7)°, and Z = 4. In compounds 3 and 5 , the palladium ions are in a distorted square planar environment. They are closely related, having two sulfur atoms of two thiosaccharinate anions, and two phosphorus atoms of one molecule of dppm or dppe, respectively, bonded to the Pd^II atom. The molecular structure of complex 3 is the first reported for a mononuclear Pd^II‐dppm‐thionate system.     

Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.     

1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe₃N)₄[(dto)₂In(dto)In(dto)₂] ( 1 ), (BzlPh₃P)₄[(dto)₂In(dto)In(dto)₂] ( 2 ), (BzlMe₃N)₃[In(dtsq)₃] ( 3 ), (Bu₄N)₃[In(dtsq)₃] ( 4 ) and (Ph₄P)[In(dtsq)₂(DMF)₂] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P2₁/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P2₁/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.     

Ein Beitrag zu Rhenium(II)‐, Osmium(II)‐ und Technetium(II)‐Thionitrosylkomplexen vom Typ [M(NS)Cl4py]—: Darstellung,Strukturen und EPR‐Spektren

A Contribution to Rhenium(II)‐, Osmium(II)‐, and Technetium(II)‐Thionitrosyl‐Complexes: Preparation, Structures, and EPR‐Spectra The reaction of [Re^VINCl₄]^— and [Os^VINCl₄]^— with S₂Cl₂ leads to the formation of the thionitrosyl complexes [M^II(NS)Cl₄]^— (M = Re, Os) which could not be isolated as pure compounds. Addition of pyridine to the reaction mixture results in the formation of the stable compounds trans‐(Ph₄P)[Os^II(NS)Cl₄py], trans‐(Hpy)[Os^II(NS)Cl₄py], trans‐(Ph₄P)[Re^II(NS)Cl₄py], and cis‐(Ph₄P)[Re^II(NS)Cl₄py]. The crystal structure analyses show for trans‐(Ph₄P)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 12.430(3)Å, b = 18.320(4)Å, c = 15.000(3)Å, β = 114.20(3)°, Z = 4), trans‐(Hpy)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 7.689(1)Å, b = 10.202(2)Å, c = 20.485(5)Å, β = 92.878(4)°, Z = 4), trans‐(Ph₄P)[Re^II(NS)Cl₄py] (triclinic, P1¯, a = 9.331(5)Å, b = 12.068(5)Å, c = 15.411(5)Å, α = 105.25(1)°, β = 90.23(1)°, γ = 91.62(1)°, Z = 2), and cis‐(Ph₄P)[Re^II(NS)Cl₄py] (monoclinic, P2₁/c, a = 10.361(1)Å, b = 16.091(2)Å, c = 17.835(2)Å, β = 90.524(2)°, Z = 4) M‐N‐S angles in the range 168‐175°. This indicates a nearly linear coordination of the NS ligand. The metal atom is octahedrally coordinated in all cases. The rhenium(II) thionitrosyl complexes (5d⁵ “low‐spin” configuration, S = 1/2) are studied by EPR in the temperature range 295 > T > 130 K. In addition to the detection of the complexes formed during the reaction of [Re^VINCl₄]^— with S₂Cl₂ EPR investigations on diamagnetically diluted powders and single crystals of the system (Ph₄P)[Re^II/Os^II(NS)Cl₄py] are reported. The ^{185, 187}Re hyperfine parameters are used to get information about the spin‐density distribution of the unpaired electron in the complexes under study. [Tc^VINCl₄]^— reacts with S₂Cl₂ under formation of [Tc^II(NS)Cl₄]^— which is not stable and decomposes under S₈ elimination and rebuilding of [Tc^VINCl₄]^— as found by EPR monitoring of the reaction.     

Effects on Coordination of Thioether Sites. 4. Structural Analysis of η3-Tripodal Ligand Manganese(I) Complexes

Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η³-{CH₃C(CH₂PPh₂)₂(CH₂SPh)-P,P′,S}Mn(CO)₃]PF₆ ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P2₁/c, R(F_o) = 0.068, R_w(F_o) = 0.055 for 3617 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)(CH₂SPh)₂-P,P′,S}Mn(CO)₃]PF₆ ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2_l, R(F_o) = 0.050, R_w(F_o) = 0.037 for 1760 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)₂(CH₂S)-P,P′,S}Mn(CO)₃] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(F_o) = 0.048, R_w(F_o) = 0.039 for 2973 reflections with I_o > 2σ(I_o). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.     

Four- and five-coordinate metal atoms in a supramolecular polymeric assembly of silver(I) with (4-methyl-2-quinolylthio)acetate

The coordination compound [Ag₂L₂(H₂O)₂] · ₂H₂O (I), L = C₁₂H₁₀NO₂S has been synthesized by the reaction of AgNO₃ with 4-methyl-2-quinolylthioacetic acid (HL) preliminarily neutralized with an equimolar amount of NBu₄OH. Its crystal structure has been determined, and luminescence properties have been studied. Crystals of I are monoclinic, space group C2/_c, _a = 31.239(6) Å, _b = 12.056(2) Å, _c = 16.846(3) Å, β = 122.17(3)°, V = 5370.4(2) ų, ρ_calc = 1.861 g/cm³, Z = 16. The structure is formed by two crystallographically nonequivalent silver atoms Ag(1) and Ag(2) and two tridentate bridging ligands L coordinated through the S, N, and O atoms. These atoms, together with water molecules, form the coordination environments of the metal atoms with CN = 5 and 4, respectively. The Ag⁺ ions and the tridentate ligands form infinite [Ag₄L₄]_n bands extended in the [001] direction. The presence of outer-sphere water molecules involved in O–H···O hydrogen bonding is responsible for the formation of a supramolecular framework structure. The photoluminescence spectrum of compound I shows two bands at ~450 and ~485 nm corresponding to the blue spectral range.     

Structural and Spectroscopic Characterization of Two New Thallium(I)/Thiosaccharinate Complexes

The crystal structures of [Tl(tsac)] ( 1 ) and [Tl(tsac)(ophen)] ( 2 ) (tsac = anion of thiosaccharin; ophen = 1, 10 phenanthroline) have been determined at 116 K by single crystal X‐ray diffractometry. Complex 1 crystallizes in the monoclinic space group P2₁/a with Z = 4 and complex 2 in the monoclinic space group C2/c with Z = 8.In both complexes T^I is coordinated to a thiosaccharinate anion through its sulphur and nitrogen atoms. A distorted eight fold coordination sphere around the cation in complex 1 is completed with two other longer Tl‐S bonds and four Tl···O contacts with five symmetry related neighbouring thiosaccharinate anions. A phenanthroline molecule acting as a bidentate ligand through its nitrogen atoms completes a four‐fold coordination around the metal atom in complex 2 . The infrared spectra of both complexes were also recorded and their most important features discussed on the basis of its structural peculiarities.     

Sulfur‐assisted Chloride and Triphenylphosphine Dissociation of Palladium(II) Complex with Phenyloxythiocarbonyl,PhOC(S), Containing Ligand: X‐Ray Structure of [Pd(PPh3)2{η1‐C(S)OPh}(Cl)]

Treatment of Pd(PPh₃)₄ with phenylchlorothionoformate, PhOC(S)Cl, in dichloromethane at ?20 °C produces the phenyloxythiocarbonyl complex [Pd(PPh₃)₂{η¹‐C(S)OPh}(Cl)], 1 . The ³¹P{¹H} NMR spectrum of 1 shows the dissociation of either the chloride or the triphenylphosphine ligand to form complex [Pd(PPh₃)₂(η²‐SCOPh)][Cl], 2 or the dipalladium complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 . Continuous stirring of the dichloromethane solution of 1 at room temperature for 4 h forms the dipalladinum complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 as the final product. Respective reactions of 1 and Et₂NCS₂Na or dppa {bis(diphenylphosphino)amine} gives complex [Pd(PPh₃){η¹‐C(S)OPh}(η²‐S₂CNEt₂)], 4 or [Pd(PPh₃){η¹‐C(S)OPh}(η²‐dppa)][Cl], 5 . Complex 1 is determined by single‐crystal X‐ray diffraction and crystallized in the monoclinic space group P2₁ with Z = 4. The cell dimensions of 1 are as follows: a = 9.5613(1) Å, b = 33.6732(3) Å, c = 12.2979(1) Å.     

Technetium Complexes with 2‐Mercapto‐methyltetrazolate

2‐Mercapto‐methyltetrazolate, Smetetraz^–, acts as monoanionic, monodentate ligand in a number of technetium compounds. Anionic Tc^V complexes of the types [TcO(Smetetraz)₄]^– and [TcN(Smetetraz)₄]^2– are formed when (Bu₄N)[Tc^VOCl₄] or (Bu₄N)[Tc^VINCl₄], respectively, react with Na(Smetetraz). Reduction of the metal takes place in the latter case. (Bu₄N)₂[TcN(Smetetraz)₄] crystallises in the monoclinic space group Pc (a = 9.701(5), b = 17.570(5), c = 16.821(10) Å, β = 96.50(3)°, Z = 2). The Tc atom is situated 0.580(3) Å above the basal plane of a square pyramid which is formed by the sulfur atoms and the nitrido ligand as its apex. The Tc–S bond lengths lie between 2.384(3) and 2.410(3) Å. [Tc(PPh₃)(Smetetraz)₃(CH₃CN)] is formed during the reaction of [TcCl₃(PPh₃)₂(CH₃CN)] with NaSmetetraz as blue needles with co‐crystallised solvent toluene (space group C2/c, a = 24.188(4), b = 14.373(1), c = 25.617(5) Å, β = 109.48(1)°, Z = 8). The metal atom is coordinated by PPh₃ and CH₃CN in the axial position of a trigonal bipyramid. All three aryl rings are on the sterically less strained side of the plane defined by the sulfur atoms. The Tc–S bond lengths range between 2.233(2) and 2.247(2) Å.     

New Rhenium(V) Nitrofuryl Semicarbazone Complexes.Crystal Structure of [ReOCl2(PPh3)(3‐(5‐Nitrofuryl)acroleine semicarbazone)]

The synthesis and characterization of the first two Re complexes with semicarbazone ligands is presented. Selected ligands are 5‐Nitro‐2‐furaldehyde semicarbazone (Nitrofurazone) ( L1 ) and its derivative 3‐(5‐Nitrofuryl)acroleine semicarbazone ( L2 ). Complexes of general formula [Re^VOCl₂(PPh₃) L ], where L = L1 and L2 , were prepared in good yields and high purity by reaction of [Re^VOCl₃(PPh₃)₂] with L in ethanol or methanol solutions. The complexes formula and molecular structures were supported by elemental analyses and electronic, FTIR, ¹H, ¹³C and ³¹P NMR spectroscopies. In addition, the crystal and molecular structure of [Re^VOCl₂(PPh₃) L2 ] was determined by X‐ray diffraction methods. [ReOCl₂(PPh₃)(3‐(5‐Nitrofuryl)acroleine semicarbazone)] crystallizes in the space group P‐1 with a = 11.2334(2), b = 11.3040(2), c = 12.5040(2) Å, α = 81.861(1), β = 63.555(1), γ = 83.626(1)°, and Z = 2. The Re(V) ion is in a distorted octahedral environment, equatorially coordinated to a deprotonated semicarbazone molecule acting as a bidentate ligand through its carbonylic oxygen and azomethynic nitrogen atoms, to an oxo ligand and a chlorine atom. The six‐fold coordination is completed by another chlorine atom and a triphenylphosphine ligand at the axial positions.     

Sr3(BS3)2 und Sr3(B3S6)2: Zwei neue nicht‐oxidische Chalkogenoborate mit trigonal‐planar koordiniertem Bor

Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂: Two Novel Non‐oxidic Chalcogenoborates with Boron in a Trigonal‐Planar Coordination The thioborates Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂ were prepared from strontium sulfide, amorphous boron and sulfur in solid state reactions at a temperature of 1123 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction. Sr₃(BS₃)₂ crystallizes in the monoclinic spacegroup C2/c (No. 15) with a = 10.187(4) Å, b = 6.610(2) Å, c = 15.411(7) Å, β = 102.24(3)° and Z = 4. The crystal structure of Sr₃(B₃S₆)₂ is trigonal, spacegroup R3¯ (Nr. 148), with a = 8.605(1) Å, c = 21.542(4) Å and Z = 3. Sr₃(BS₃)₂ contains isolated [BS₃]^3— anions with boron in a trigonal‐planar coordination. The strontium cations are found between the layers of orthothioborate anions. Sr₃(B₃S₆)₂ consists of cyclic [B₃S₆]^3— anions and strontium cations, respectively.     

Synthesis and Structural Study of Copper(I) or Silver(I) Complexes of 2,11‐Dithia‐4,5,6,7,8,9‐Hexahydro[3.3]paracyclophanes

The complexes of 2,11‐dithia‐4,5,6,7,8,9‐hexahydro[3.3]paracyclophane (dthhpcp) with Cu(I), i.e. [Cu₂I₂(dthhpcp)₂]·2H₂O 1 , or with Ag(I), i.e. [Ag(dthhpcp)(NO₃)]thf 2 and [Ag(dthpcp)(CF₃COO)] 3 , were prepared for structural study by single‐crystal X‐ray diffraction analysis. For these three complexes, dthhpcp serves as a bridging group in the polymeric structure through bridging sulfur atoms via metal, while the bonding of anion with the second metal atom forms the multi‐diminished structures. Complex 1 is a novel two‐dimensional coordination polymer composed of Cu₆ motifs, in which Cu₂I₂ formed a square planar unit to link the dthhpcp molecule. The two oxygen atoms of the nitrate anion as a bridge for two Ag atoms in complex 2 provides a three‐dimensional channel framework of silver(I) with a tetrahydrofuran molecule as a guest inside the open cavities. In contrast, the analogous reaction with silver triflouroacetate gave a complex 3 , which is composed of infinite linear chains of‐Ag‐dthhpcp‐Ag‐dthhpcp‐ along the a axis. Unit cell data: complex 1 , orthorhombic system, space group P2(1)2(1)2(1), a = 19.2982(11) Å b = 16.5661(10) Å, c = 25.3006(15) Å, β = 90°, Z = 8; complex 2 , orthorhombic system, space group Pna2(1), a = 8.8595(6) Å, b = 12.6901(9) Å, c = 19.8449(14) Å, β = 90°, Z = 4; complex 3 , monoclinic system, space group P2(1)/n, a = 8.845(3) Å, b = 20.841(6) Å, c = 11.061(3) Å, β = 107.832(6)°, Z = 4.     

X‐Ray Crystal Structures and Quantum Chemical Calculations of Tetraphenyl‐arsonium Tetraazidoaurate(III) and Azido(triphenylphosphine)Gold(I)

The single crystal X‐ray structure determinations are reported for [Ph₄As][Au(N₃)₄] ( 1 ) and Ph₃PAuN₃ ( 2 ). Compound 1 is an ionic species with a “windmill” shaped anion. It crystallizes in the monoclinic space group C2/c, a = 18.396(2), b = 6.2492(4), c = 23.555(2) Å; β = 107.98(1)°, Z = 4, R1_{(all data)} = 0.0227, wR2 = 0.0374. The lattice parameters of compound 2 , which crystallizes in the orthorhombic space group P2₁2₁2₁, are a = 10.9252(1), b = 11.5642(1), c = 13.0993(1) Å; Z = 4, R1_{(all data)} = 0.0176, wR = 0.0334. The experimentally obtained X‐ray data and vibrational frequencies of both compounds were compared with those calculated at B3LYP/LANL2DZ and B3LYP/SDD level of theory and for 1 also at the MP2/SDD level.     

Palladium(II) Complexes with the Mixed‐Donor Ligand CH3S‐(CH2)3‐PPh2 Crystal Structures of [PdCl2{CH3S‐(CH2)3‐PPh2}n](n = 1, 2)

The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by ¹H NMR and ¹³C NMR. Reactions of S‐P3 with [PdCl₂(PhCN)₂] afforded the complexes [PdCl₂(S‐P3)] ( I ) and [PdCl₂(S‐P3)₂] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P2₁/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)ų, Z = 4. Likewise, compound II crystallizes in monoclinic space group P2₁/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)ų, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom.     

Three- and four-coordinated silver(I) ions in the coordination polymers [Ag(Me<Subscript>4</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript> and [Ag(2,3-Et<Subscript>2</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript>

The coordination polymers [AgPF₆(Me₄Pyz)₂] (I) and [AgPF₆(2,3-Et₂Pyz)₂] (II) were synthesized, and their structures were determined. Crystals of I are monoclinic, space group C2/c, a = 10.213(2) Å, b = 16.267(3) Å, c = 12.663(3) Å, β = 92.90(3)°, V = 2102.1(7) ų, ρ_calcd = 1.660 g/cm³, Z = 4. The structure of I is built of polymeric zigzag [Ag(C₈H₁₂N₂)] _∞ ⁺ chains and octahedral [PF₆] anions. The coordination polyhedron of the Ag⁺ ion is a flat triangle. Crystals of II are tetragonal, space group P \(\bar 4\)2(1)/c,a = b = 10.641(1) Å, c = 18.942(1) Å, V = 2144.6(2) ų, ρ_calcd = 1.627 g/cm³, Z = 4. In the structure of II, 2D cationic layers of fused square rings exist; the rings consist of four Ag⁺ cations linked by four bridging ligands of diethylpyrazine Et₂Pyz. The coordination polyhedron of the Ag⁺ ion is an irregular four-vertex polyhedron.     

Synthesis and structural characterization of acetatobis(triphenylphosphine)dicarbonylrhenium(I). new car☐ylato derivatives of rhenium(I)

Acetatobis(triphenylphosphine)dicarbonylrhenium (I), (PPh₃)₂(CO)₂Re(O₂CCH₃), has been prepared in a novel way by treating (PPh₃)₂(CO)₂Re(NHCOR) (R = C₆H₅, p-MeC₆H₄) with triethylamine and water in the presence of air. Oxidation of the ethyl group of the tertiary amine is presumably involved in the formation of the acetate ligand. Three-dimensional single-crystal X-ray diffraction analysis shows that the complex is octahedral with the phosphines in trans positions and the acetate ion acting as a chelating ligand. The complex crystallizes in theP2₁/c space group with cell dimensions a = 17.63(2), b = 9.72(1), c = 20.95(2)Å, β = 104°38'(6'), Z = 4. The mean values of bond lengths observed are Re-P 2.415, Re-O 2.21 and Re-(CO) 1.85Å. The same acetate derivative and a series of car?ylato complexes (PPh₃)₂(CO)₂Re(O₂CR') have been obtained from reactions of Re(CO)₂(PPh₃)₃H with car?ylic acids R'COOH (R' = H, CH₃, CH₂Cl, CH₂CH₃, C₆H₅). When trifluoroacetic acid is used, a product of formula (PPh₃)₂(CO)₃Re(OC(O)CF₃) is isolated. The action of neutral ligands L on some of these products gave rise to derivatives of formula (PPh₃)₂(CO)₂(L)Re(OC(O)R') (L = CO, R' = H, CH₃, C₆H₅; L = pMeC₆H₄NC, R' = CH₃), having monodentate car?ylato moieties.     

N,N-Dialkylcarbamato Complexes of the d10 cations of copper,silver, and gold

The reaction of CuO'Bu with CO₂, and ⁱPr₂NH in the presence of PPh₃, gives the dialkylcarbamato complex [Cu(O₂CNⁱPr₂)(PPh₃)₂] ( 1 ). The CO₂/R₂NH system (R = Me, Et) in an appropriate organic medium reacts with Ag₂O giving the corresponding N,N-dialkylcarbamato complexes of analytical formula [Ag(C₂CNR₂)] (R = Me, 2 ; R = Et, 3 ). The methyl derivative 2 was characterized by X-ray diffraction methods. Crystal data of 2 : for [Ag₂(O₂CNMe₂)₂], C₆H₁₂Ag₂N₂O₄, mol. wt. 391.9; monoclinic, space group P2₁/c, a = 12.08(1), b = 3.797(2), c = 11.316(7) Å, β = 113.37(6)°, V = 476.3 ų, Z = 2, D_c = 2.732 g cm^?3; μ(MoK_α) = 40.64 cm^?1, F(000) = 376.0; R = 0.059, R_w = 0.067; g.o.f. 1.27. The structure consists of dinuclear [(Ag₂OCNMe₂)₂] units with slightly distorted linearly two-coordinated Ag-atoms containing bridging carbamato groups to form a substantially planar eight-membered ring with an intra-annular Ag? Ag distance of 2.837(2) Å; the dinuclear units are further joined by Ag? O bonds to form an infinite array. Compound 3 , which is presumably dinuclear, as suggested by cryoscopic measurements in benzene, undergoes a structural fission with PPh₃, giving the mononuclear triphenylphosphine derivative [Ag(O₂CNEt₂)(PPh₃)₂] ( 4 ). The amine-catalyzed conversion of Ag₂O into Ag₂CO₃, in the presence of the ⁱPr₂NH/CO₂ system, is also reported. Cl-Exchange from [AuCl(PPh₃)] with [Ag(O₂CNEt₂)] ( 3 ) gives the first N,N-dialkylcarbamato complex of gold, namely [Au(O₂CNEt₂)(PPh₃)] ( 5 ), which crystallizes in the monoclinic system: C₂₃H₂₅AuNO₂P · 0.5 C₇H₁₆, mol. wt. 625.5, space group P2₁/c; a = 13.212(5), b = 12.25(1), c = 16.795(6) Å, β = 109.09(2)°, V = 2568(2) Å₃, Z = 4, D_c, = 1.618 g cm^?3; μ(AgK_α) = 31.40 cm^?1, F(000) = 1236.0; R = 0.058; R_w = 0.064; g.o.f. 2.121. The compound contains two-coordinated Au-atom, namely to the P-atom and to the O-atom of the monodentate carbamato group, the P? Au? O bond angle being 174.7(3)°. The reaction with MeI showed these compounds to react predominantly at the carbamato O-atom giving the corresponding urethanes R₂NCO₂Me. Evidence was gathered for the transient coordination of CO to Ag in 3 .     

Syntheses,Structures and Spectroscopic Studies of Silver(I) Coordination Polymers Bridged by Flexible Bidentate Ligands

The reaction of Ag₂SO₄ and bpp (bpp = 1,3‐bis(4‐pyridyl)propane) in H₂O afforded the complex [Ag₂(bpp)₂(SO₄) · 6.5H₂O·CH₃OH]_n, 1. The IR and TGA have been recorded and the structure has been determined. Crystal data for 1: Space group C₂/c, a = 17.885(4), b = 25.230(6), c = 8.832(2) Å, β = 105.437(4)°. V = 3841(1) ų, Z = 8 with final residuals R1 = 0.0710 and wR2 = 0.1620. The complex shows a three‐dimensional supramoleclar structure constructed with two‐dimensional infinite [Ag₂(bpp)₂]_n sheetlike layers pillared by Ag‐Ag interactions and Ag····O (SO₄) interactions in the solid state.