One-dimensional polymeric chlorocadmate(II) systems of N-methylpiperazinium and N,N′-dimethylpiperazinium compounds: synthesis, structural and thermal properties

The chlorocadmate(II) systems of (H₂me₂pipz)[Cd₂Cl₆(H₂O)₂] (1) and (H₂mepipz)₂[Cd₃Cl₁₀(H₂O)] (2) (L = me₂pipz = N,N′-dimethylpiperazine; L′ = mepipz = N-methylpiperazine) were prepared and their structural and thermal properties investigated. Compound 1 is monoclinic, space group P2₁/c, A = 7.664(1), B = 7.472(4), C = 15.347(1) Å, β = 99.468(7)°, Z = 2, R = 0.024. The crystal structure consists of organic cations and infinite one-dimensional chains of [CdCl₃(H₂O)]_n³⁻ anions. Each Cd atom is octahedrally surrounded by bridged and terminal chlorine atoms and by a water molecule, which is in trans position with respect to the terminal chlorine atom. Inter- and intrachain hydrogen bond interactions between the terminal chlorine atoms and the water molecules contribute to the crystal packing. Compound 2 is orthorhombic, space group Cmc2₁, A = 15.286(3), B = 13.354(3), C = 13.154(3) Å, R = 0.023. The crystal structure consists of organic dications and infinite chains of [Cd₂Cl₆(CdCl₄H₂O]_n⁴⁻ units running along the [001] axis. Each unit is formed of regularly alternate six-coordinated Cd atoms, one of them linking one pentacoordinated Cd atom which completes its coordination througha water molecule. A strong hydrogen bond interaction involving the organic dication and the inorganic chain contributes to the crystal packing. Differential hydrogen bond interaction involving the organic dication and the inorganic chain contributes to the crystal packing. Differential scanning calorimetry measurements did not show the presence of any structural phase transitions. The structures are compared with those of (H₂pipz)[Cd₂Cl₆(H₂O)₂] (3), (H₂mepipz)[Cd₂Cl₆(H₂O)₂]·H₂O (4) and (H₂mepipz)[Cd₂Cl₆] (5) (L = pipz = piperazine, L′ = mepipz = N-ethylpiperazine).     

The synthesis and reactions of A-ring aromatic steroid complexes of manganese tricarbonyl

Treatment of the A-ring aromatic steroids estrone 3-methyl ether and β-estradiol 3, 17-dimethyl ether with Mn(CO)₅⁺BF₄⁻ in CH₂Cl₂ yields the corresponding [(steroid)Mn(CO)₃]BF₄ salts 1 and 2 as mixtures of and β isomers. The X-ray structure of [(estrone 3-methyl ether)Mn(CO)₃]BF₄ · CH₂Cl₂ (1) having the Mn(CO)₃ moiety on the side of the steroid is reported: space group P2₁ with a=10.3958(9), b=10.9020(6), c=12.6848(9) Å, β=111.857(6)°, Z=2, V=1334.3(2) ų, _calc=.481 cm⁻³, R=0.0508, and wR=0.0635. The molecule has the traditional ‘piano stool’ structure with a planar arene ring and linear Mn---C---O linkages. The nucleophiles NaBH₄ and LiCH₂C(O)CMe₃ add to [(β-estradiol 3,17-dimethyl ether)Mn(CO)₃]BF₄ (2) in high yield to give the corresponding - and β-cyclohexadienyl manganese tricarbonyl complexes (3). The nucleophiles add meta to the arene -OMe substituent and exo to the metal. The and β isomers of 3 were separated by fractional crystallization and the X-ray structure of the β isomer with an exo-CH₂C(O)CMe₃ substituent is reported (complex 4): space group P2₁2₁2₁ with a=7.5154(8), b=15.160(2), c=25.230(3) Å, Z=4, V=2874.4(5) ų, _calc=1.244 g cm⁻³, R=0.0529 and wR2=0.1176. The molecule 4 has a planar set of dienyl carbon atoms with the saturated C(1) carbon being 0.592 Å out of the plane away from the metal. The results suggest that the manganese-mediated functionalization of aromatic steroids is a viable synthetic procedure with a range of nucleophiles of varying strengths.     

Ruthenium complexes containing tertiary phosphines and imidazole or 2,2′-bipyridine ligands

Complexes RuCl₃(PPh₃)L₂ (L = MeIm (1a, Im (1b)) and [RuCl₂(PPh₃)₂(bipy)]Cl·4H₂O (2) have been synthesized via the ruthenium(III) precursor RuCl₃(PPh₃)₂ (DMA), and characterized, including an X-ray structural analysis for 1a (MeIm = N-methylimidazole, Im = imidazole, bipy = 2,2′-bipyridyl, and DMA = N, N′-dimethylacetamide). Crystals of 1a are monoclinic, space group P2₁/n, A = 10.5491(5), B = 20.4934(9), C = 12.8285(4) Å, β = 90.166(4)°, Z = 4. The structure, which reveals a mer configuration for the chlorides, and cis-methylimidazoles, was solved by conventional heavy atom methods and was refined by full-matrix least-square procedures to R = 0.041 and R_w = 0.042 for 3328 reflections with I 3σ(I). From the RuCl₂(PPh₃)₃ precursor, the ruthenium(II) complexes RuCl₂(PPh₃)₂L₂ and [RuCl(PPh₃)L₄]Cl have been made (L = Im or MeIm), while [RuCl(dppb)Im₃]Cl has been made from [RuCl₂(dppb)]₂(μ-dppb) (dppb = Ph₂P(CH₂)₄PPh₂).     

1,10-Phenanthroline-5,6-dione as a building block for the synthesis of homo- and heterometallic complexes

1,10-Phenanthroline-5,6-dione (C₁₂H₆N₂O₂ (1)) reacts with V(η⁶-mesitylene)₂ and Ti(η⁶-toluene)₂ affording coordination compounds of general formula M(O,O′---C₁₂H₆N₂O₂)₃ (M=Ti (2); M=V (3)) which further react with TiCl₄ or TiCp₂(CO)₂ yielding the tetrametallic species M(O,O′---C₁₂H₆N₂O₂---N,N′)₃(M′L_n)₃ (M=V, M′L_n=TiCl₄ (4); M=Ti, M′L_n=TiCp₂ (5); M=V, M′L_n=TiCp₂ (6)). The complex salt [Fe(N,N′---C₁₂H₆N₂O₂)₃][PF₆]₂ (7) has been obtained from iron(II) chloride tetrahydrate and 1 in the presence of NH₄PF₆. The reaction of 7 with TiCp₂(CO)₂ affords the tetrametallic derivative [Fe(N,N′---C₁₂H₆N₂O₂---O,O′)₃(TiCp₂)₃][PF₆]₂ (8). TiCl₂(THF)₂ reacts with MCp₂(O,O′---C₁₂H₆N₂O₂) to give MCp₂(O,O′---C₁₂H₆N₂O₂---N,N′)TiCl₂ (M=Ti (9); M=V (10)). By reaction of TiCp₂(O,O′---C₁₂H₆N₂O₂---N,N′)TiCl₂ (9) with C₁₂H₆N₂O₂, the bimetallic derivative TiCp₂(O,O′---C₁₂H₆N₂O₂---N,N′)TiCl₂(O,O′---C₁₂H₆N₂O₂) (11) has been prepared, which readily adds to TiCl₄, to give the trimetallic titanium derivative TiCp₂(O,O′---C₁₂H₆N₂O₂---N,N′)TiCl₂(O,O′---C₁₂H₆N₂O₂---N,N′)TiCl₄ (12). VCp₂(O,O′---C₁₂H₆N₂O₂---N,N′)TiCl₂ (10) reacts with the tris-chelate iron(II) cation 7 affording the heptametallic cationic complex [Fe(N,N′---C₁₂H₆N₂O₂---O,O′)TiCl₂(N,N′---C₁₂H₆N₂O₂---O,O′)VCp₂]₃ ⁺² isolated as the hexafluorophosphate 13.     

Kinetics and mechanisms of ligand substitution reactions of molybdenum SO2 complexes. Synthesis and X-ray structure of trans-Mo(CO)2 (dmpe) (PPh3) (SO2)

Kinetic results are reported for intramolecular PPh₃ substitution reactions of Mo(CO)₂(η¹-L)(PPh₃)₂(SO₂) to form Mo(CO)₂(η²-L)(PPh₃)(SO₂) (L = DMPE = (Me)₂PC₂H₄P(Me)₂ and dppe=Ph₂PC₂H₄PPh₂) in THF solvent, and for intermolecular SO₂ substitutions in Mo(CO)₃(η²-L)(η²-SO₂) (L = 2,2′-bipyridine, dppe) with phosphorus ligands in CH₂Cl₂ solvent. Activation parameters for intramolecular PPh₃ substitution reactions: ΔH^≠ values are 12.3 kcal/mol for dmpe and 16.7 kcal/mol for dppe; ΔS^≠ values are −30.3 cal/mol K for dmpe and −16.4 cal/mol K for dppe. These results are consistent with an intramolecular associative mechanism. Substitutions of SO₂ in MO(CO)₃(η²-L)(η²-SO₂) complexes proceed by both dissociative and associative mechanisms. The facile associative pathways for the reactions are discussed in terms of the ability of SO₂ to accept a pair of electrons from the metal, with its bonding transformations of η²-SO₂ to η¹-pyramidal SO₂, maintaining a stable 18-e count for the complex in its reaction transition state. The structure of Mo(CO)₂(dmpe)(PPh₃)(SO₂) was determined crystallographically: P2₁/c, A=9.311(1), B = 16.344(2), C = 18.830(2) Å, ß=91.04(1)°, V=2865.1(7) ų, Z=4, R(F)=3.49%.     

X-ray crystal structure of Cu2(medpco-2H)Cl2, (medpco = N,N′-bis(2-N,N-dimethylaminoethyl)pyridine-2,6-dicarboxamide 1-oxide. Copper(II) complexes of a deprotonated binucleating pyridine N-oxide ligand

The X-ray structure is reported for the complex Cu₂(medpco-2H)Cl₂, (medpco = N,N′-bis-N,N-dimethylaminoethyl)pyridine-2,6-dicarboxamide 1-oxide. The complex is triclinic, , a=8.313(4), B=11.403(5), C=11.611(3) Å, =91.66(3), β=108.99(4), γ=109.60(3)° and Z=2. The deprotonated ligand (medpco-2H)²⁻ acts as a binulceating ligand, producing an N-oxide-bridged complex. Each copper in Cu₂(medpco-2H)Cl₂ is five-coordinate, being coordinated by a bridging N-oxide oxygen, a deprotonated amide nitrogen, a tertiary amine nitrogen and two bridging chlorides. The complex does not exhibit significant magnetic interaction, and this may be the result of distortion of the bridging geometry from planarity. A range of other, apparently N-oxide-bridged, complexes of the type Cu₂(medpco-2H)X₂ is reported. The complex Cu₂(medpco-2H)Br₂·H₂O is strongly antiferromagnetic, with magnetic data closely fitting the expected binuclear structure.     

A dicopper complex of N,N′-bis[2,2-dimethyl-4-(2-hydroxyphenyl)-3-aza-3-buten] oxamide. Structure and magnetic behaviour of the mono hydrated form

The ligand N, N′-bis[2,2-dimethyl-4-(2-hydroxyphenyl)-3-aza-3-buten] oxamide with two identical coordination sites reacts with copper ions in its tetradeprotonated form to yield the dinuclear complex [Cu₂(C₂₄H₂₆N₄O₄)]·H₂O. The structure of this compound has been determined by the X-ray diffraction method. The crystals are orthorhombic with a = 11.744(1), B = 16.369(2), C = 26.340(3) Å, V = 5064(1) ų, Z = 8, space group Pbca. The oxamide is in a trans conformation with two different environments for the copper centres, a (4 + 1) coordination mode for the first one and a square planar environment for the other one. The water molecule is not directly bound to a copper centre, but involved in hydrogen bonding with the two oxygen atoms of an N₂O₂ coordination site. Indeed, extra coordination comes from a phenolic oxygen atom belonging to an adjacent dinuclear unit. Static susceptibility measurements point to a strong intrapair antiferromagnetic exchange interaction of 2J = −520(±4) cm⁻¹ and possibly an interpair ferromagnetic exchange interaction of 10(±5) cm⁻¹.     

Crystal growth in aqueous hydrofluoric acid and (HF)x · pyridine solutions: syntheses and crystal structures of [Ni(H2O)6][MF6] (M = Ti, Zr, Hf) and Ni3(py)12F6 · 7H2O

The syntheses and structures of [Ni(H₂O)₆]²⁺[MF₆]²⁻ (M = Ti,Zr,Hf) and Ni₃(py)₁₂F₆·7H₂O are reported. The former three compounds are isostructural, crystallizing in the trigonal space group (No. 148) with Z = 3. The lattice parameters are a = 9.489(4), C = 9.764(7) Å, with V = 761(1) ų for Ti; a = 9.727(2), C = 10.051(3) Å, with V = 823.6(6) ų for Zr; and a = 9.724(3), C = 10.028(4)Å, with V = 821.2(8)ų for Hf. The structures consist of discrete [Ni(H₂O)₆]²⁺ and [MF₆]²⁻ octahedra joined by O---HF hydrogen bond Large single crystals were grown in an aqueous hydrofluoric acid solution. Ni₃(py)₁₂F₆·7H₂O crystallizes in the monoclinic space group I2/a (No. 15) with Z = 4. The lattice parameters are a = 16.117(4), B = 8.529(3), C = 46.220(7) Å, β = 92.46(2)°, and V = 6348(5) ų. The structure consists of discrete Ni(py)₄F₂ octahedra linked through H---O---HF and H---O---HO hydrogen bonding interactions. Single c were grown from a (HF)_x·pyridine/pyridine/water solution.     

Dinuclear silver(I) complexes of 24-membered bibracchial tetraimine Schiff base macrocycles derived from 2,5-diformylthiophene

The cyclocondensation of 2,5-diformylthiophene and the amines N,N-bis-(2-aminoethyl)-2-phenylethylamine, N,N-bis-(2aminoethyl)-t-butyl-amine and N,N-bis-(2-aminoethyl)-t-butyl-amine in the presence of silver(I) salts yields homodinuclear bibracchial tetraimine Schiff base macrocyclic complexes. The structures of two such complexes are also reported. The complex Ag₂L⁴(NO₃)(PF₆) (2) crystallises in the triclinic space group , No. 2) and has unit-cell dimensions a = 12.834(6), B = 13.183(6), C = 14.588(7) Å, = 64.86(4), β = 79.77(4), γ = 69.44(3)° with Z = 2; there is a monodentate and singly bridging nitrate anion present and the Ag---Ag separation is 4.161 Å. The complex Ag₂L⁴(CH₃CN)₂(BF₄)₂·CH₃CN (9) crystallises in the triclinic space group , No. 2) and has unit-cell dimensions a = 9.297(4), B = 12.985(3), C = 21.770(5) Å, = 91.570(10), β = 92.33(3), γ = 97.92(3) ° with Z = 2; there is a strongly bonded acetonitrile molecule coordinated to each silver atom and the Ag---Ag separation is 4.920 Å.     

Studies of the oxovanadium(IV)—oxalate system: syntheses and crystal structures of binuclear (Ph4P)2[(VO)2(H2O)2(C2O4)3]·4H2O and of the one-dimensional chain material, (Ph4P)[VOCl(C2O4)]

The hydrothermal reactions of (Ph₄P)[VO₂Cl₂] and H₂C₂O₄ at 150 and 125°C yield (Ph₄P)₂[V₂O₂(H₂O)₂(C₂O₄)₃]·4H₂O (1) and (Ph₄P)[VOCl(C₂O₄)] (2), respectively. The structure of the molecular anion of 1 consists of a binuclear unit of oxovanadium(IV) octahedra bridged by a bisbidentate oxalate group. The VO₆ coordination geometry at each vanadium site is defined by a terminal oxo group, an aquo ligand, and four oxygen donors — two from the bisbidentate bridging oxalate and two from the terminal bidentate oxalate. The structure of 2 consists of discrete Ph₄P⁺ cations occupying regions between [VOCl(C₂O₄)]⁻_∞ spiral chains. The structure of the one-dimensional anionic chain exhibits V(IV) octahedra bridged by bisbidentate oxalate groups. Crystal data: 1·4H₂O, monoclinic P2₁/n, A = 12.694(3), B = 12.531(3), C = 17.17(3) Å, β = 106.32(2)°, V = 2621.3(13) ų, Z = 2, D_calc = 1.501 g cm⁻³, structure solution and refinement converged at a conventional residual of 0.0518; 2, tetragonal P4₃, A = 12.145(2), C = 15.991(3) Å, V = 2358.7(12) ų, Z = 4, R = 0.0452.     

Alkene rotation in [Ru(η-C5H5) (L2) (η-alkene][CF3SO3] with L2 = iPr- or pTol-diazabutadiene. X-ray crystal structure of [Ru(η-C5H5(pTol-DAB) (η-ethene][CF3SO3]

Reaction of RuCl(η⁵-C₅H₅(pTol-DAB) with AgOTf (OTf = CF₃SO₃) in CH₂Cl₂ or THF and subsequent addition of L′ (L′ = ethene (a), dimethyl fumarate (b), fumaronitrile (c) or CO (d) led to the ionic complexes [Ru(η⁵-C₅H₅)(pTol-DAB)(L′)][OTf] 2a, 2b and 2d and [Ru(η⁵-C₅H₅)(pTol-DAB)(fumarontrile-N)][OTf] 5c. With the use of resonance Raman spectroscopy, the intense absorption bands of the complexes have been assigned to MLCT transitions to the iPr-DAB ligand. The X-ray structure determination of [Ru(η⁵-C₅H₅)(pTol-DAB)(η²-ethene)][CF₃SO₃] (2a) has been carried out. Crystal data for 2a: monoclinic, space group P2₁/n with A = 10.840(1), b = 16.639(1), C = 14.463(2) Å, β = 109.6(1)°, V = 2465.6(5) ų, Z = 4. Complex 2a has a piano stool structure, with the Cp ring η⁵-bonded, the pTol-DAB ligand σN, σN′ bonded (Ru-N distances 2.052(4) and 2.055(4) Å), and the ethene η²-bonded to the ruthenium center (Ru-C distances 2.217(9) and 2.206(8) Å). The C = C bond of the ethene is almost coplanar with the plane of the Cp ring, and the angle between the plane of the Cp ring and the double of the ethene is 1.8(0.2)°. The reaction of [RuCl(η⁵-C₅H₅)(PPh)₃ with AgOTf and ligands L′ = a and d led to [Ru(η⁵-C₅H₅)(PPh₃)₂(L′)]OTf] (3a) and (3d), respectively. By variable temperature NMR spectroscopy the rottional barrier of ethene (a), dimethyl fumarate (b and fumaronitrile (c) in complexes [Ru(η⁵-C₅H₅)(L₂)(η²-alkene][OTf] with L₂ = iPr-DAB (a, 1b, 1c), pTol-DAB (2a, 2b) and L = PPh₃ (3a) was determined. For 1a, 1b and 2b the barrier is 41.5±0.5, 62±1 and 59±1 kJ mol⁻¹, respectively. The intermediate exchange could not be reached for 1c, and the ΔG^# was estimated to be at least 61 kJ mol⁻. For 2a and 3a the slow exchange could not be reached. The rotational barrier for 2a was estimated to be 40 kJ mol⁻. The rotational barier for methyl propiolate (HC≡CC(O)OCH₃) (k) in complex [Ru(η⁵-C₅H₅)(iPr-DAB) η²-HC≡CC(O)OCH₃)][OTf] (1k) is 45.3±0.2 kJ mol⁻¹. The collected data show that the barrier of rotational of the alkene in complexes 1a, 2a, 1b, 2b and 1c does not correlate with the strength of the metal-alkene interaction in the ground state.     

The synthesis and structural characterization of carborane oligomers connected by carbon-carbon and carbon-boron bonds between icosahedra

The reaction of dilithiated o-carborane (closo-1,2-Li₂-1,2-C₂B₁₀H₁₀) with CuCl₂ gives 1,1′-bis(o-carborane) (1), 1,3′-bis(o-carborane) (2) and 1,4′-bis(o-carborane) (3). Compound 2 (C₄B₂₀H₂₂) crystallizes in the monoclinic space group P2₁/n with A = 6.9275(6), B = 9.7655(8), C = 12.356(1) Å, β = 90.028(2)° and Z = 2. The structure was solved by direct methods and refined to R = 0.048 and R_w = 0.074. Compound 3 (C₄B₂₀H₂₂) crystallizes in the orthorhombic space group P2₁2₁2₁ with A = 6.8854(5), B = 12.523(1), C = 19.847(1) Å and Z = 4. The structure was solved by direct methods and refined to R = 0.078 and R_w = 0.091. The coupling reaction of dilithiated m-carborane (closo-1,7-Li₂-1,7-C₂B₁₀H₁₀) with CuCl₂ results in the formation of 1,1′-bis(m-carborane) (4) and tetra(m-carborane) (5).     

Synthesis of one dimensional tin selenides in supercritical amines

Three new crystalline tin selenide salts have been prepared from the reactions of [PPh₄]₂[Sn(Se₄₃] in supercritical solvents. The starting material pyrolyzes in supercritical acetonitrile to form [PPh₄]₄[Sn₆Se₂₁] (I), and it also reacts with SnSe in supercritical ammonia leading to a mixture of [PPh₄]₄[Sn₃Se₁₁]₂ (II). and [PPh₄]₂[Sn(Se₄)(Se₆)₂] (III). All three compounds have been characterized by single crystal X-ray diffraction. Crystallographic data: for I, C₉₆H₉₀P₄Se₂₁Sn₆, space group triclinic, P-1, A = 18.763(3), B = 24.600(4), C = 13.137(1) Å, = 102.63(1), β = 93.66(1), γ = 108.72(1)°, V = 5544(1) ų, Z = 2, R = 0.0350, R_W = 0.0317: for II, C₉₆H₈₀P₄Se₂₂Sn₆, space group monoclinic P2₁/c, A = 31.500(4), B = 16.572(3), C = 22.352(3) Å, β = 103.53(1)°, V = 11344(3) ų, Z = 4, R = 0.0771, R_W = 0.0664: for III, C₄₈H₄₀P₂Se₁₆Sn, space group monoclinic, C2/c, A = 25.381(2), B = 13.934(4), C = 19.465(3) Å, β = 121.587(8)°, V = 5867(2) ų, Z = 4, R = 0.0807, R_W = 0.0650. One of the compounds, [PPh₄]₂[Sn(Se₄(Se₆₂], is a molecular cluster while the other two complexes [PPh₄]₄[Sn₃Se₁₁]₂ and [PPh₄]₄[Sn₆Se₂₁], are one dimensional tin selenide chains. The structures of the two chains are related and consits of tetrahedral and distorted trigonal bipyramidal tin(IV) centers bridged by Se²⁻, Se₂²⁻ and Se₃²⁻ chains.     

Molecular structures and some properties of tris(2-aminoethyl) amine cobalt(III) complexes with thiocarboxylato-O,S such as 3-mercaptopropionato, 2-mercaptoacetato and their derivatives

Cobalt(III) complexes with a thiolate or thioether ligand, t-[Co(mp)(tren)]⁺ (2), t-[Co(mtp)(tren)]²⁺ (1Me) and t-[Co(mta)(tren)]²⁺ (2Me), (mp = 3-mercaptopropionate, MA = 3-(methylthio)propionate and MTA = 2-(methylthio)acetate) have been prepared in aqueous solutions. The crystal structures of 1, 2, 1Me and 2Me were determined by X-ray diffraction methods. The crystal data are as follows, t-[Co(mp)(tren)]ClO₄ (1CIO₄): monoclinic, P2₁/n, A = 10.877(8), B = 11.570(4), c = 12.173(7) Å, β = 92.20(5)°, V = 1531(1) ų, Z = 4 and R = 0.060; t-[Co(ma)(tren)]Cl·3H₂O (2Cl·3H₂O): monoclinic, P2₁/n, a = 7.7688(8), B = 27.128(2), C = 7.858(1) Å, β = 100.63(1)°, V = 1627.7(3) ų, Z = 4 and R = 0.066; (+)₄₆₅^CD-t-[Co(mtp)(tren)](ClO₄)₂ ((+)₄₆₅^CD-1Me(ClO₄)₂): orthorhombic, P2₁2₁2₁, A = 10.6610(7), B = 11.746(1), C = 15.555(1) Å, V = 1947.9(3) ų, Z = 4 and R = 0.068; (+)₄₆₅^CD-t-[Co(mta)(tren)](ClO₄)₂ ((+)₄₆₅^CD-2Me(ClO₄)₂): orthorhombic, P2₁2₁2₁, a = 10.564(1), B = 11.375(1), C = 15.434(2) Å, V = 1854.7(4) ų, Z = 4 and R = 0.047. All central Co(III) atoms have approximately octahedral geometry, coordinated by four N, one O, and one S atoms. All of the complexes are only isomer, of which the sulfur atom in the didentate-O,S ligands are located at the trans position to the tertiary amine nitrogen atom of tren. 1 and 1Me contain six-membered chelate ring, and 2 and 2Me do five-membered chelate ring in the didentate ligand. The chirality of the asymmetric sulfur donor atom in (+)₄₆₅^CD-1Me is the S configuration and that in (+)₄₆₅^CD-2Me is the R one. The ¹H NMR, ¹³C NMR and electronic absorption spectral behaviors and electrochemical properties of the present complexes are discussed in relation to their stereochemistries.     

Synthesis and problematic crystal structures of [Al(CH3CN)6][MCl6]3(CH3CN)3 (M=Ta, Nb or Sb)

Compounds of formula [Al(CH₃CN)₆][MCl₆]₃(CH₃CN)₃ (M=Ta (1); Nb (2); Sb (3)) have been synthesized from the reactions of MCl₅ and AlCl₃ in acetonitrile and characterized by X-ray crystallography. Complex 1 crystallizes in the tetragonal space group P4/mbm with a = B = 10.408(2), C = 7.670(3) Å, V = 830.9(4) ų and Z = 2/3. Complex 2 crystallizes in the tetragonal space group P4/mnc with a = B = 330(a), C = 15.320(3) ų V = 1634.8(4) ų and Z = 4/3. Complex 3 also crystallizes in the tetragonal space group P4/mnc with a = B = 10.313(1), C = 15.238(2) Å, V = 1621.0(1) ų and Z = 4/3. The non-integer Z values for complexes 1–3 result unusual problems of disorder and/or twinning in these crystal structures due to their high symmetry. The M---Cl distances range from 2.329(3) Å in the Ta complex to 2.355(1) Å in the Sb complex, while the Al---N distances are similar in all three complexes, ranging from 1.92(1) to 1.97(1) Å, respectively. Complexes 1–3 are the first structurally characterized complexes that contain a (hexaacetonitrile)aluminum(III) cation.     

The ReH6[P(C6H5)3]2 ion as a ligand: complexes with M(CO)3 fragments (M = Cr, Mo, W)

The reactions of [(H₅C₆)₃P]₂ReH₆⁻ with (CH₃CN)₃Cr(CO)₃, (diglyme)Mo(CO)₃ or (C₃H₇CN)₃W(CO)₃ led to the formation of [(H₅C₆)₃P]₂ReH₆M(CO)₃⁻ (M = Cr, Mo, W) complexes. These have been characterized by IR and NMR spectroscopies, as well as elemental analyses. A single crystal X-ray diffraction study has also been carried out for the M = Cr complex as a K(18-crown-6)⁺ salt. The complex crystallizes as a THF monosolvate in the monoclinic space group P2₁/n with a = 22.323(6), B = 9.523(2), C = 27.502(5) Å, β = 104.98(2)⁰ and V = 5648 ų for Z = 4. The Re---Cr separation is 2.5745(12) Å, and the two phosphine ligands are oriented unsymmetrically. Although the hydride ligands were not found, the presence of three bridging hydrides and a dodecahedral coordination geometry about rhenium could be inferred. Low temperature ¹H and ³¹P NMR spectroscopic studies did not reveal the low symmetry of the solid state structure.     

Selective addressing of heteroditopic ligands by iron(II) and platinum(II)

The heteroditopic ligand 4′-(4,7,10-trioxadec-1-yn-10-yl)-2,2′:6′,2″-terpyridine, 2, contains an N,N′,N″-donor metal-binding domain that recognizes iron(II), and a terminal alkyne site that selectively couples to platinum(II). This selectivity has been used to investigate routes to the formation of heterometallic systems. The single crystal structures of ligand 2 and the complex [Fe(2)₂][PF₆]₂ are reported.     

Multinucleating ligands from multiple palladium(0)-catalysed cross-coupling reactions — synthesis and characterisation of a trinuclear cyclometallated ruthenium(II) complex and a hexanuclear EPR-active molybdenum complex

Two multinucleating ligands have been prepared from 1,3,5-tris(3,5-dibromophenyl)benzene by multiple Pd(0)-catalysed cross-coupling reactions. 1,3,5-Tris[3,5-bis(4-pyridylethenyl)phenyl]benzene (L¹) has six remote pyridyl moieties, each of which can coordinate a 17 valence-electron Mo(tp^*)(NO)Cl fragment (tp^* = hydrotris(3,5-dimethylpyrazolyl)borate), affording the hexanuclear complex [Cl(NO)(tp^*)Mo₆(L¹) (1). 1,3,5-Tris[3,5-bis(2-pyridyl)phenyl]benzene (L²) incorporates three potentially terdentate, cyclometallating N,C,N-donor sets, and can coordinate three Ru(tpy)²⁺ fragments (tpy = 2,2′:6′,2″-terpyridine) giving the trinuclear complex [(tpy)Ru₃(L²)][PF₆]₃ (2). Complex 1 is EPR active, with nearest-neighbour pairs of molybdenum centres displaying magnetic exchange interactions. Electrochemical studies of the two complexes suggest that there is little ground-state interaction between the metal centres in either case.     

Synthesis and characterization of SrCu2(O2CR)3(bdmap)3 and Bi2(O2CCH3)4(bdmap)2(H2O) (R = CH3, CF3; bdmap = 1,3-bis(dimethylamino)-2-propanolato)

New mixed metal complexes SrCu₂(O₂CR)₃(bdmap)₃ (R = CF₃ (1a), CH₃ (1b)) and a new dinuclear bismuth complex Bi₂(O₂CCH₃)₄(bdmap)₂(H₂O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF₂ and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi₂O₃ at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm⁻¹. Crystal data for 1a: C₂₇H₅₁N₆O₉F₉Cu₂Sr/THF, monoclinic space group P2₁/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) ų, Z = 2; for 1b: C₂₇H₆₀N₆O₉Cu₂Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) ų, Z = 8; for 2: C₂₂H₄₈O₁₁N₄Bi₂, monoclinic space group P2₁/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) ų, Z = 4.     

Application of the hydro(solvo)thermal technique to the synthesis of metal carbonyl chalcogenide clusters Part 3. Synthesis, structural characterization, and spectroscopic studies of the clusters [{M(CO)4}n(MS4)] (M = Mo, W; N=1, 2)

The methanothermal reactions of M(CO)₆ (M = Mo, W) with Na₂S₂ gave a series of homonuclear clusters [{M(CO)₄}_n(MS₄)]²⁻ (M=Mo, W; N=1, 2), i.e. (Ph₄P)₂[(CO)₄Mo(MoS₄)] (I), (Ph₄P)₂[(CO)₄W(WS₄)] (II), (Ph₄P)₂[(CO)₄Mo(MoS₄)Mo(CO)₄] (III) and (Ph₄P)₂[(CO)₄W(WS₄)W(CO)₄] (IV). The two dimers, I and II, as well as the two trimers, III and IV, are isostructural to each other, respectively. All compounds crystallize in the triclinic space group with Z=2. The cell dimensions are: a=12.393(8), b=19.303(9), c=11.909(6) Å, =102.39(5), β=111.54(5), γ=73.61(5)°, V=2522(3) ų at T=23 °C for I; a=12.390(3), b=19.314(4), c=11.866(2) Å, =102.66(2), β=111.49(1), γ=73.40(2)°, V=2511(1) ų at T=23 °C for II; a=11.416(3), b=22.524(4), c=10.815(4) Å, =91.03(2), β=100.57(3), γ=88.96(2)°, V=2733(1) ų at T=−100 °C for III, a=11.498(1), b=22.600(4), c=10.864(3) Å, =90.92(2), β=100.85(1), γ=88.58(1)°, V=2771(2) ų at T=23 °C for IV. The dimers are each formed by the coordination of the tetrathiometalate as a bidentate chelating ligand to an M(CO)₄ fragment while addition of another M(CO)₄ fragment to the dimers results in the trimers. All compounds contain both tetrahedral and octahedral metal centers with the formal 6+ and 0 oxidation states, respectively.