Radical salts of bis(ethylenediseleno)tetrathiafulvalene with paramagnetic tris(oxalato)metalate anions

The synthesis, crystal structure, and physical characterization of five new radical salts formed by the organic donor bis(ethylenediseleno)tetrathiafulvalene (BEST) and the paramagnetic tris(oxalato)metalate anions [M(C2O4)3]3- (M = FeIII and CrIII) are reported. The salts isolated are (BEST)4[M(C2O4)3].PhCOOH.H2O with MIII = Cr (1) or Fe (2) (crystal data: 1, triclinic, space group P(-)1 with a = 14.0999(4) A, b = 15.3464(4) A, c =19.5000(4) A, alpha = 76.711(5) degrees, beta = 71.688(5) degrees, gamma = 88.545(5) degrees, V = 3893.5(2) A3, and Z = 2; 2, triclinic, space group P(-)1 with a = 14.0326(3) A, b =15.1981(4) A, c =19.4106(4) A, alpha = 76.739(5) degrees, beta = 71.938(5) degrees, gamma = 88.845(5) degrees, V = 3824.9(2) A3, and Z = 2), (BEST)4[M(C2O4)3].1.5H2O with MIII = Cr (3) or Fe (4) (crystal data: 3, monoclinic, space group C2/m with a = 33.7480(10) A, b =12.3151(7) A, c = 8.8218(5) A, beta = 99.674(5) degrees, V = 3614.3(3) A3, and Z = 2; 4, monoclinic, space group C2/m with a = 33.659(6) A, b =12.248(2) A, c = 8.759(2) A, beta = 99.74(3) degrees, V = 3558.9(12) A3, and Z = 2), and (BEST)9[Fe(C2O4)3]2.7H2O (5) (crystal data: triclinic, space group P(-)1 with a =12.6993(3) A, b =18.7564(4) A, c = 18.7675(4) A, alpha = 75.649(5) degrees, beta = 107.178(5) degrees, gamma = 79.527(5) degrees, V = 3977.5(3) A3, and Z = 1). The structures of all these salts consist of alternating layers of the organic donors and tris(oxalato)metalate anions. In 1 and 2 the anionic layers contain also benzoic acid molecules H-bonded to the terminal oxygen atoms of the anions. In all salts the organic layers adopt beta-type packings. Along the parallel stacks the donors form dimers in 3 and 4, trimers in 5, and tetramers in 1 and 2. All the compounds are paramagnetic semiconductors with high room-temperature conductivities and magnetic susceptibilities dominated by the Fe- or Cr-containing anions.     

Unexpected formation of an azetidine-carborane derivative by dehydration of N-(1,12-dicarba-closo-dodecaboran-1-yl)formamide. The first X-ray structure of a 2,3-bis(imino)azetidine

Efforts to dehydrate (1,12-dicarba-closo-dodecaboran(12)-1-yl)formamide (a = 6.685(2) A, b = 12.877(4) A, c = 12.547(4) A, alpha = gamma = 90 degrees, beta = 90.724(11) degrees, V = 1080.8(6) A(3), Z = 4) resulted in the formation of a series of unexpected products. Addition of the Burgess reagent to the formamide, for example, led to the isolation of the corresponding methyl carbamate (a = 11.529(8) A, b = 11.529(8) A, c = 11.402(12) A, alpha = beta = gamma = 90 degrees, V = 1516(2) A(3), Z = 4), while treatment with triphosgene, a well-known dehydrating agent, resulted in the formation of a highly unusual 2,3-bis(p-carboranylimino)azetidine derivative. This particular compound, in the presence of Re(I), was hydrolyzed to give the corresponding amide, which is the first example of a 2,3-bis(imino)azetidine that has been characterized crystallographically (a = 38.496(13) A, b = 11.920(4) A, c = 27.523(10) A, beta = 127.050(5) degrees, V = 10079(6) A(3), Z = 8).     

Synthesis and Characterization of Water-Soluble 1,2-Bis(bis(hydroxyalkyl)phosphino)ethane Ligands and Their Nickel(II), Ruthenium(III), and Rhodium(I) Complexes

The syntheses of the water-soluble, chelating phosphines 1,2-bis(bis(hydroxybutyl)phosphino)ethane (1, n = 3; DHBuPE) and 1,2-bis(bis(hydroxypentyl)phosphino)ethane (1, n = 4; DHPePE) are reported. These ligands (and, in general, other 1,2-bis(bis(hydroxyalkyl)phosphino)ethane ligands) can be used to impart water solubility to metal complexes. As examples of this, the [Ni(DHPrPE)(2)Cl]Cl (2), [Rh(DHPrPE)(2)][Cl] (3), and [Ru(DHBuPE)(2)Cl(2)][Cl] (4) complexes were synthesized; they are indeed soluble in water (>0.5 M). Crystals of DHPrPE (1, n = 2) are monoclinic, space group P2(1)/c, with a = 9.5935(8) ?, b = 9.353(2) ?, c = 10.655(2) ?, alpha = 90 degrees, beta = 100.03(1) degrees, gamma = 90, V = 941.5(5) ?(3), R = 0.051, and Z = 2. Crystals of [Ni(DHPrPE)(2)Cl]Cl (2) are monoclinic, space group I2, with a = 15.951(3) ?, b = 11.454(2) ?, c = 20.843(3) ?, alpha = 90 degrees, beta = 91.24(2) degrees, gamma = 90 degrees, V = 3807(2) ?(3), R = 0.062, and Z = 4. Crystals of [Rh(DHPrPE)(2)][Cl] (3) are triclinic, space group P&onemacr;, with a = 13.900(2) ?, b = 15.378(2) ?, c = 18.058(2) ?, alpha = 87.71(1) degrees, beta = 75.03(1) degrees, gamma = 85.24(1), V = 3715(2) ?(3), R = 0.044, and Z = 4. Crystals of [Ru(DHBuPE)(2)Cl(2)][Cl] (4) are monoclinic, space group C2/c, with a = 14.310(2) ?, b = 21.630(2) ?, c = 15.459(3) ?, alpha = 90 degrees, beta = 99.83(1) degrees, gamma = 90, V = 4715(1) ?(3), R = 0.056, and Z = 4.     

Reactivity of rhenium(V) oxo Schiff base complexes with phosphine ligands: rearrangement and reduction reactions

The symmetric rhenium(V) oxo Schiff base complexes trans-[ReO(OH2)(acac2en)]Cl and trans-[ReOCl(acac2pn)], where acac2en and acac2pn are the tetradentate Schiff base ligands N,N'-ethylenebis(acetylacetone) diimine and N,N'-propylenebis(acetylacetone) diimine, respectively, were reacted with monodentate phosphine ligands to yield one of two unique cationic phosphine complexes depending on the ligand backbone length (en vs pn) and the identity of the phosphine ligand. Reduction of the Re(V) oxo core to Re(III) resulted on reaction of trans-[ReO(OH2)(acac2en)]Cl with triphenylphosphine or diethylphenylphosphine to yield a single reduced, disubstituted product of the general type trans-[Re(III)(PR3)2(acac2en)]+. Rather unexpectedly, a similar reaction with the stronger reducing agent triethylphosphine yielded the intramolecularly rearranged, asymmetric cis-[Re(V)O(PEt3)(acac2en)]+ complex. Reactions of trans-[Re(V)O(acac2pn)Cl] with the same phosphine ligands yielded only the rearranged asymmetric cis-[Re(V)O(PR3)(acac2pn)]+ complexes in quantitative yield. The compounds were characterized using standard spectroscopic methods, elemental analyses, cyclic voltammetry, and single-crystal X-ray diffraction. The crystallographic data for the structures reported are as follows: trans-[Re(III)(PPh3)2(acac2en)]PF6 (H48C48N2O2P2Re.PF6), 1, triclinic (P), a = 18.8261(12) A, b = 16.2517(10) A, c = 15.4556(10) A, alpha = 95.522(1) degrees , beta = 97.130(1) degrees , gamma = 91.350(1) degrees , V = 4667.4(5) A(3), Z = 4; trans-[Re(III)(PEt2Ph)2(acac2en)]PF6 (H48C32N2O2P2Re.PF6), 2, orthorhombic (Pccn), a = 10.4753(6) A, b =18.4315(10) A, c = 18.9245(11) A, V = 3653.9(4) A3, Z = 4; cis-[Re(V)O(PEt3)(acac2en)]PF6 (H33C18N2O3PRe.1.25PF6, 3, monoclinic (C2/c), a = 39.8194(15) A, b = 13.6187(5) A, c = 20.1777(8) A, beta = 107.7730(10) degrees , V = 10419.9(7) A3, Z = 16; cis-[Re(V)O(PPh3)(acac2pn)]PF6 (H35C31N2O3PRe.PF6), 4, triclinic (P), a = 10.3094(10) A, b =12.1196(12) A, c = 14.8146(15) A, alpha = 105.939(2) degrees , beta = 105.383(2) degrees , gamma = 93.525(2) degrees , V = 1698.0(3) A3, Z = 2; cis-[Re(V)O(PEt2Ph)(acac2pn)]PF6 (H35C23N2O3PRe.PF6), 5, monoclinic (P2(1)/n), a = 18.1183(18) A, b = 11.580(1) A, c = 28.519(3) A, beta = 101.861(2) degrees , V = 5855.9(10) A(3), Z = 4.     

Tris(1,2-dimethyl-3-hydroxy-4(1H)-pyridone)oxotantalum(v): a new water-soluble tantalum complex containing the [Ta=O]3+ core

The synthesis, the characterization and the X-ray crystal structure of a novel tantalum(v) complex tris(1,2-dimethyl-3-hydroxy-4(1H)-pyridone)oxotantalum(v) [TaO(C7H8O2N)3] 1 is reported. Starting from the tantalum pentaethoxide a two-step reaction was carried out observing rigorous anhydrous conditions in methanol in the first step, while the insertion of the oxo group was achieved using water as oxygen donor in the second step. X-Ray diffraction analysis of a crystal of 1 obtained upon evaporation of an aqueous solution shows a seven-coordinate monomeric complex containing the [Ta=O]3+ core in the triclinic space group P1, a = 7.282(3), b = 14.055(5), c = 16.987(6) A, alpha = 65.704(5), beta = 89.155(6), gamma = 75.270(6) degrees, V = 1525(1)A3, Z = 2. Spectroscopic investigation reveals that the complex is highly soluble and stable in water at physiological pH values; as a consequence the complex may represent a potential candidate for the development of new studies on aqueous tantalum(v) chemistry for radiopharmaceutical applications.     

Synthesis, characterization, and spontaneous resolution of chiral nickel(II) complexes with the tripod ligand tris[2-(((2-phenylimidazol-4-yl)methylidene)amino)ethyl]amine

The chiral nickel(II) complexes of a tripod-type ligand with the chemical formulas [Ni(H3L)](NO3)2.MeOH (1), [Ni(H3L)](ClO4)2.MeOH (2), and [Ni(H3L)](C6H5COO)2.6H2O (3) were synthesized and characterized (H3L = tris[2-(((2-phenylimidazol-4-yl)methylidene)amino)ethyl]amine). The crystal structures of 1-3 were determined by their single-crystal X-ray analyses. 1, C37H40N12O7Ni: orthorhombic, P2(1)2(1)2(1); a = 14.198(2) A, b = 22.422(2) A, c = 12.019(2) A, Z = 4. 2, C37H40N10O9Cl2Ni: orthorhombic, P2(1)2(1)2(1); a = 14.206(2) A, b = 22.735(3) A, c = 12.696(3) A, Z = 4. 3, C50H58N10O10Ni: triclinic, P1; a = 14.191(5) A, b = 16.048(4) A, c = 13.692(4) A, alpha = 115.25(2) degrees, beta = 111.07(3) degrees, gamma = 64.75(2) degrees, Z = 2. Each complex has an octahedral coordination environment for the nickel(II) ion, formed by the six nitrogen donor atoms, and is either a delta (clockwise) or a lambda (anticlockwise) enantiomorph, depending on the screw arrangement of the tripod-type ligand around the nickel(II) ion. The circular dichroism (CD) spectrum of a powdered sample of a crystal of 1 showed a positive and a negative peak at 915 and 630 nm, respectively, and that of another crystal showed an enantiomeric pattern. The observation of the Cotton effect and the crystal structure provided evidence for spontaneous resolution of the chiral complex molecule.     

Synthesis and Structures of Sb[N(H)(C(6)H(2)(t)Bu(3))](3) and Bi[N(H)(C(6)H(2)(t)Bu(3))](3): Implications for the Steric Limits of Supermesityl Substitution

Syntheses and isolations of the tris(amino)stibine and tris(amino)bismuthine E[N(H)(C(6)H(2)(t)Bu(3))](3) (E = Sb, Bi) from ECl(3) and LiN(H)(C(6)H(2)(t)Bu(3)) are described, together with spectroscopic and structural characterization [crystal data for C(54)H(90)N(3)Sb, M = 903.04, space group P&onemacr;, a = 11.491(5) ?, b = 24.652(7) ?, c = 10.002(5) ?, alpha = 98.38(3) degrees, beta = 96.44(5) degrees, gamma = 77.25(3) degrees, V = 2724(2) ?(3), D(c) = 1.101 Mg/m(3), Z = 2, R = 0.0547; crystal data for C(54)H(90)BiN(3), M = 990.27, space group P&onemacr;, a = 11.511(5) ?, b = 24.785(15) ?, c = 9.981(5) ?, alpha = 98.06(5) degrees, beta = 96.50(4) degrees, gamma = 77.40(5) degrees, V = 2742(2) ?(3), D(c) = 1.200 Mg/m(3), Z = 2, R = 0.0619]. The compounds bear the "bulky" 2,4,6-tri-tert-butylphenyl substituent (known as supermesityl or Mes), and their formation is considered in the context of the same reactions for PCl(3) and AsCl(3), which have been previously shown to produce the aminoiminopnictine structures [N(H)(C(6)H(2)(t)Bu(3))]P=N(C(6)H(2)(t)Bu(3)) and [N(H)(C(6)H(2)(t)Bu(3))]As=N(C(6)H(2)(t)Bu(3)). The observations establish the limits of the steric control by the supermesityl substituent and provide qualitative support for the thermodynamic significance of substituent steric strain.     

Bis(pyrazol-1-yl)acetates as tripodal heteroscorpionate ligands in iron chemistry: syntheses and structures of iron(II) and iron(III) complexes with bpza, bdmpza, and bdtbpza ligands

The molecular structure of the previously reported species "[Fe(bdtbpza)Cl]" has been revealed by X-ray structure determination to be a ferrous dimer [Fe(bdtbpza)Cl](2) (2c) [bdtbpza = bis(3,5-di-tert-butylpyrazol-1-yl)acetate]. The syntheses of ferrous 2:1 complexes [Fe(bpza)(2)] (3a) and [Fe(bdtbpza)(2)] (3c) as well as ferric 1:1 complexes [NEt(4)][Fe(bpza)Cl(3)] (4a) and [NEt(4)][Fe(bdmpza)Cl(3)] (4b) [bpza = bis(pyrazol-1-yl)acetate, bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate] are reported. Complexes 3a, previously reported [Fe(bdmpza)(2)] (3b), and 3c are high-spin. No spin crossover to the low-spin state was observed in the temperature range of 5-350 K. 4a and 4b are synthesized in one step and in high yield from [NEt(4)](2)[Cl(3)FeOFeCl(3)]. 4a and 4b are iron(III) high-spin complexes. Crystallographic information: 2c (C(24)H(39)ClFeN(4)O(2).CH(2)Cl(2).CH(3)CN) is triclinic, P1, a = 12.171(16) A, b = 12.851(14) A, c = 13.390(13) A, alpha = 98.61(9) degrees, beta = 113.51(11) degrees, gamma = 108.10(5) degrees, Z = 2; 3a (C(8)H(7)Fe(0.5)N(4)O(2)) is monoclinic, P2(1)/n, a = 7.4784(19) A, b = 7.604(3) A, c = 16.196(4) A, beta = 95.397(9) degrees, Z = 4; 3c (C(24)H(39)Fe(0.5)N(4)O(2)) is monoclinic, P2(1)/n, a = 9.939(6) A, b = 18.161(10) A, c = 13.722(8) A, beta = 97.67(7) degrees, Z = 4; 4b (C(20)H(35)Cl(3)FeN(5)O(2)) is monoclinic, C2/c, a = 30.45(6) A, b = 12.33(2) A, c = 16.17(3) A, beta = 118.47(5) degrees, Z = 8.     

Copper(I) complexes, copper(I)/O(2) reactivity, and copper(II) complex adducts, with a series of tetradentate tripyridylalkylamine tripodal ligands

Copper(I) and copper(II) complexes possessing a series of related ligands with pyridyl-containing donors have been investigated. The ligands are tris(2-pyridylmethyl)amine (tmpa), bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine (pmea), bis[2-(2-pyridyl)ethyl]-(2-pyridyl)methylamine (pmap), and tris[2-(2-pyridyl)ethyl]amine (tepa). The crystal structures of the protonated ligand H(tepa)ClO(4), the copper(I) complexes [Cu(pmea)]PF(6) (1b-PF(6)), [Cu(pmap)]PF(6) (1c-PF(6)), and copper(II) complexes [Cu(pmea)Cl]ClO(4).H(2)O (2b-ClO(4).H(2)O), [Cu(pmap)Cl]ClO(4).H(2)O (2c-ClO(4).H(2)O), [Cu(pmap)Cl]ClO(4) (2c-ClO(4)), and [Cu(pmea)F](2)(PF(6))(2) (3b-PF(6)) were determined. Crystal data: H(tepa)ClO(4), formula C(21)H(25)ClN(4)O(4), triclinic space group P1, Z = 2, a = 10.386(2) A, b = 10.723(2) A, c = 11.663(2) A, alpha = 108.77(3) degrees, beta = 113.81(3) degrees, gamma = 90.39(3) degrees; 1b-PF(6), formula C(19)H(20)CuF(6)N(4)P, orthorhombic space group Pbca, Z = 8, a = 14.413(3) A, b = 16.043(3) A, c = 18.288(4) A, alpha = beta = gamma = 90 degrees; (1c-PF(6)), formula C(20)H(22)CuF(6)N(4)P, orthorhombic space group Pbca, Z = 8, a = 13.306(3) A, b = 16.936(3) A, c = 19.163(4) A, alpha = beta = gamma = 90 degrees; 2b-ClO(4).H(2)O, formula C(19)H(22)Cl(2)CuN(4)O(5), triclinic space group P1, Z = 4, a = 11.967(2) A, b = 12.445(3) A, c = 15.668(3) A, alpha = 84.65(3) degrees, beta = 68.57(3) degrees, gamma = 87.33(3) degrees; 2c-ClO(4).H(2)O, formula C(20)H(24)Cl(2)CuN(4)O(5), monoclinic space group P2(1)/c, Z = 4, a = 11.2927(5) A, b = 13.2389(4) A, c = 15.0939(8) A, alpha = gamma = 90 degrees, beta = 97.397(2) degrees; 2c-ClO(4), formula C(20)H(22)Cl(2)CuN(4)O(4), monoclinic space group P2(1)/c, Z = 4, a = 8.7682(4) A, b = 18.4968(10) A, c = 13.2575(8) A, alpha = gamma = 90 degrees, beta = 94.219(4) degrees; 3b-PF(6), formula [C(19)H(20)CuF(7)N(4)P](2), monoclinic space group P2(1)/n, Z = 2, a = 11.620(5) A, b = 12.752(5) A, c = 15.424(6) A, alpha = gamma = 90 degrees, beta = 109.56(3) degrees. The oxidation of the copper(I) complexes with dioxygen was studied. [Cu(tmpa)(CH(3)CN)](+) (1a) reacts with dioxygen to form a dinuclear peroxo complex that is stable at low temperatures. In contrast, only a very labile peroxo complex was observed spectroscopically when 1b was reacted with dioxygen at low temperatures using stopped-flow kinetic techniques. No dioxygen adduct was detected spectroscopically during the oxidation of 1c, and 1d was found to be unreactive toward dioxygen. Reaction of dioxygen with 1a-PF(6), 1b-PF(6), and 1c-PF(6) at ambient temperatures leads to fluoride-bridged dinuclear copper(II) complexes as products. All copper(II) complexes were characterized by UV-vis, EPR, and electrochemical measurements. The results manifest the dramatic effects of ligand variations and particularly chelate ring size on structure and reactivity.     

Copper(I) ion mediated self-organization of molecular rectangular boxes from 1,2-Bis(2-pyridylethynyl)benzene Ligands with bulky substituents

The reaction of chiral 1,2-bis(2-pyridylethynyl)benzene ligands with copper(I) ions in dichloromethane at room temperature gives rise to the formation of molecular rectangular boxes in high yields. The structures of these complexes were confirmed by X-ray crystallographic analysis. The compound CL1 crystallizes in the triclinic space group P1, with a = 13.707(4) A, b = 14.891(3) A, c = 12.030(1) A, alpha = 101.65(2) degrees, beta = 115.08(2) degrees, gamma = 97.66(1) degrees, V = 2110.8(2) A(3), Z = 1 (T = 288 K). The compound CL2 crystallizes in the triclinic space group P1, with a = 13.539(4) A, b = 14.755(2) A, c = 11.951(2) A, alpha = 101.70(1) degrees, beta = 115.11(1) degrees, gamma = 97.44(2) degrees, V = 2053.8(8) A(3), Z = 1 (T = 198 K). The formation of box-type structure is caused by steric hindrance between bulky substituents of the ligands.     

Novel copper(II) induced formation of a porphyrinogen derivative: X-ray structural,spectroscopic, and electrochemical studies of porphyrinogen complexes of Cu(II) and Co(III) complex of a trispyrazolyl tripodal ligand

Copper(II) complexes of a novel pyrazole containing porphyrinogen and cobalt(III) and zinc(II) complexes of a pyrazole containing tripodal ligand having N-donor atoms have been investigated. 5-Methyl-3-formylpyrazole (MPA) on reaction with copper(II) nitrate or perchlorate in the presence of tris(2-aminoethyl)amine (tren) forms novel pyrazole-based porphyrinogen complexes [Cu(T(3)-porphyrinogen)(H(2)O)](NO(3))(2) (1a) and [Cu(T(3)-porphyrinogen)(H(2)O)](ClO(4))(2) (1b) where T(3)-porphyrinogen is 1,6,11,16-tetraaza-5,10,15,20-tetrahydroxy-2,7,12,17-tetramethylporphyrinogen. The same products are also obtained when tren is replaced by triethylamine. By contrast, the reaction between MPA, tren, and cobalt(II) perchlorate produces the cobalt(III) complex [Co(HMPz(3)tren)]ClO(4) (2) derived from the tripodal Schiff base tris[4-(3-(5-methyl-pyrazolyl)-3-aza-3-butenyl]amine (H(3)MPz(3)tren). The X-ray crystal structures of the copper(II) complexes (1a and 1b) and the cobalt(III) complex (2) have been determined. The structures show distorted square pyramidal coordination environments for 1a and 1b with the water molecule occupying the apical site, while for complex 2 a distorted octahedral geometry is obtained. Data for 1a follow: a = 19.476(3) A, b = 9.4116(8) A, c = 14.204(3) A; alpha = 90 degrees = gamma, beta = 107.58(2) degrees; V = 2482.0(7) A(3), Z = 4. Data for 1b follow: a = 20.967(3) A, b = 9.1563(18) A, c = 14.858(4) A; alpha = 90 degrees = gamma, beta = 108.44(3) degrees; V = 2706.0(10) A(3), Z = 4. Data for 2 follow: a = 21.293(3) A, b = 12.724(2) A, c = 19.777(4) A; alpha = 90 degrees = gamma, beta = 93.03(2) degrees; V = 5350.6(15) A(3), Z = 8. All three complexes crystallize in the monoclinic crystal system with the C2/c space group. The complexes are further characterized by UV-vis, IR, EPR, and electrochemical studies.     

Reaction of bis(phosphine)(hydrotris(3,5-dimethylpyrazolyl)borato)rhodium(I) with phenylacetylene,p-nitrobenzaldehyde,and triphenyltin hydride: structures of [Rh(Tp)(PPh(3))(2)], [Rh(Tp)(H)(C(2)Ph)(P(4-C(6)H(4)F)(3))], [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PPh(3))], and [Rh(Tp)(H)(SnPh(3))(PPh(3))

The complexes [Rh(Tp)(PPh(3))(2)] (1a) and [Rh(Tp)(P(4-C(6)H(4)F)(3))(2)] (1b) combine with PhC(2)H, 4-NO(2)-C(6)H(4)CHO and Ph(3)SnH to give [Rh(Tp)(H)(C(2)Ph)(PR(3))] (R = Ph, 2a; R = 4-C(6)H(4)F, 2b), [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PR(3))] (R = Ph, 3a), and [Rh(Tp)(H)(SnPh(3))(PR(3))] (R = Ph, 4a; R = 4-C(6)H(4)F, 4b) in moderate to good yield. Complexes 1a, 2b, 3a, and 4a have been structurally characterized. In 1a the Tp ligand is bidentate, in 2b, 3a, and 4a it is tridentate. Crystal data for 1a: space group P2(1)/c; a = 11.9664(19), b = 21.355(3), c = 20.685(3) A; beta = 112.576(7) degrees; V = 4880.8(12) A(3); Z = 4; R = 0.0441. Data for 2b: space group P(-)1; a = 10.130(3), b = 12.869(4), c = 17.038(5) A; alpha = 78.641(6), beta = 76.040(5), gamma = 81.210(6) degrees; V = 2100.3(11) A(3); Z = 2; R = 0.0493. Data for 3a: space group P(-)1; a = 10.0073(11), b = 10.5116(12), c = 19.874(2) A; alpha = 83.728(2), beta = 88.759(2), gamma = 65.756(2) degrees; V =1894.2(4) A(3); Z = 2; R = 0.0253. Data for 4a: space group P2(1)/c; a = 15.545(2), b = 18.110(2), c = 17.810(2) A; beta = 95.094(3) degrees; V = 4994.1(10) A(3); Z = 4; R = 0.0256. NMR data ((1)H, (31)P, (103)Rh, (119)Sn) are also reported.     

Verdazyl radicals as oligopyridine mimics: structures and magnetic properties of M(II) complexes of 1,5-dimethyl-3-(2,2'-bipyridin-6-yl)-6-oxoverdazyl (M = Mn,Ni, Cu,Zn)

The verdazyl radical 1,5-dimethyl-3-(2,2'-bipyridin-6-yl)-6-oxoverdazyl (3) was prepared, and its homoleptic metal complexes M(3)(2)(2+).2X(-) (5, M = Mn(II); 6, M = Ni(II); 7, M = Cu(II); 8, M = Zn(II); X = ClO(4), PF(6)) were characterized by single-crystal X-ray diffraction and variable-temperature magnetic susceptibility measurements. Relevant crystallographic parameters are as follows: 5, monoclinic space group Pna2(1), a = 18.755(4) A, b = 11.154(3) A, c = 16.594(4) A, alpha = 90.00 degrees, beta = 90.00 degrees, gamma = 90.00 degrees, V = 3471.4(13) A(3), and Z = 4; 7, triclinic space group Ponedblac;, a = 9.4638(18) A, b = 9.8442(19) A, c = 18.769(4) A, alpha = 103.746(3) degrees, beta = 92.925(3) degrees, gamma = 94.869(3) degrees, V = 1687.8(6) A(3), and Z = 2; 8, triclinic space group Ponedblac;, a = 9.4858(14) A, b = 9.7919(14) A, c = 18.889(3) A, alpha = 104.196(3) degrees, beta = 92.855(3) degrees, gamma = 94.216(3) degrees, V = 1692.1(4) A(3), and Z = 2. In all cases, the two verdazyl-based ligands bind almost perpendicular to each other in meridional positions, yielding pseudooctahedral metal complexes whose general structural features are strongly reminiscent of metal bis(terpyridine) complexes. The intramolecular metal-verdazyl magnetic exchange coupling is strongly ferromagnetic in 6 (J(Ni-vd) = +240 cm(-1)), and strongly antiferromagnetic in 5 (J(Mn-vd) = -93 cm(-1)). Complex 7 exhibits weak ferromagnetic coupling (J(Cu-vd) = -4.5 cm(-1)). Intramolecular radical-radical coupling in the zinc complex 8 was found to be weakly antiferromagnetic (J(vd-vd) = -8 cm(-1)). Intramolecular radical-radical exchange was generally weak in the four metal complexes, ranging from -10 cm(-1) (for 5) to +2 cm(-1) (for 7). The low-temperature magnetic behavior of 7 and 8 is complex, possibly arising from a combination of intra- and intermolecular interactions.     

Synthesis, structures, and magnetic properties of heterodimetal bis(mu-hydroxo)chromium(III)nickel(II) complexes with Tpa derivatives having sterically bulky substituents

A series of heterodinuclear bis(mu-hydroxo)chromium(III)nickel(II) complexes was newly prepared: [(phen)(2)Cr(mu-OH)(2)Ni(tpa)](ClO(4))(3) x 0.5H(2)O (1), [(phen)(2)Cr(mu-OH)(2)Ni(Me-tpa)](ClO(4))(3) x 2H(2)O (2), [(phen)(2)Cr(mu-OH)(2)Ni(Me(2)-tpa)](ClO(4))(3) x 2H(2)O (3), and [(phen)(2)Cr(mu-OH)(2)Ni(Me(3)-tpa)](ClO(4))(3) x 3H(2)O (4), where phen is 1,10-phenanthroline and tpa, Me-tpa, Me(2)-tpa, and Me(3)-tpa are tris(2-pyridylmethyl)amine, [(6-methyl-2-pyridyl)methyl]bis(2-pyridylmethyl)amine, bis[(6-methyl-2-pyridyl)methyl](2-pyridylmethyl)amine, and tris[(6-methyl-2-pyridyl)methyl]amine, respectively. X-ray crystallography revealed that the structures of 1-4 resemble one another having an edge-shared bioctahedral structure with a Cr(mu -OH)(2)Ni unit (crystal data: 1 x C(2)H(5)OH, triclinic, P1, a = 13.179(4) A, b = 13.685(4) A, c = 14.260(4) A, alpha = 84.95(2) degrees, beta = 77.65(1) degrees, gamma = 90.21(2) degrees, V = 2502(1) A(3), Z = 2, R = 0.103, R(w) = 0.097; 2 x C(2)H(5)OH, triclinic, P1, a = 13.214(2) A, b = 13.657(2) A, c = 14.417(3) A, alpha = 95.205(5) degrees, beta = 102.583(4) degrees, gamma =90.720(3) degrees, V = 2527.3(8) A(3), Z = 2, R = 0.090, R(w) = 0.122; 3 x C(2)H(5)OH, triclinic, P1, a = 13.276(2) A, b =13.696(2) A, c = 14.454(2) A, alpha = 95.640(3) degrees, beta = 102.821(4) degrees, gamma = 90.174(3) degrees, V = 2549.5(6) A(3), Z = 2, R= 0.087, R(w)= 0.119; 4, triclinic, P1, a = 10.8916(9) A, b = 14.268(2) A, c = 17.522(2) A, alpha = 84.498(9) degrees, beta = 74.313(7) degrees, gamma = 72.402(7) degrees, V = 2498.6(5) A(3), Z = 2, R = 0.060, R(w)= 0.088). Chromium and nickel ions are coordinated by two phen's and Me(n)-tpa, respectively, to complete a distorted octahedral coordination sphere. Introduction of the 6-methyl group(s) onto the pyridyl group(s) results in the elongation of the Ni-N bond distances due to an unfavorable steric interaction between the methyl group and the bridging hydroxide group: systematic elongation of the Ni-N bond distances and the Cr ...Ni separations accompanied by an increase in the Cr-O-Ni angles was observed as the number of the methyl groups increases. Variable-temperature magnetic susceptibility measurements of 1-4 (4.2-300 K) indicated that magnetic interactions between Cr(III) and Ni(II) ions are systematically modulated from a very weak antiferromagnetic interaction to a ferromagnetic interaction as the number of the methyl groups increases; the exchange integrals J's for 1-4 are estimated to be -1.4, +0.0, +4.1, and +7.4 cm(-1), respectively. The magneto-structural relationship is discussed in terms of the change in the magnetic orbital energies of nickel(II) centers arising from the change in the Ni-N bond distances.     

Synthesis,structure, and redox properties of the extremely crowded triarylpnictogens: tris(2,4,6-triisopropylphenyl)phosphine,arsine, stibine,and bismuthine

A series of the extremely crowded triarylpnitogens, tris(2,4,6-triisopropylphenyl)phosphine (1), arsine (2), stibine (3), and bismuthine (4), were synthesized by the reaction of 2,4,6-triisopropylphenylcopper(I) with the corresponding pnictogen trichlorides. Introducion of the three bulky aryl groups resulted in the unusual structures and redox properties, which were studied by X-ray crystallography and cyclic voltammetry. The triarylpnictogens 1, 2, and 3 had extremely large bond angles around pnictogen atoms (1: 111.5 degrees , 2: 109.2 degrees , 3: 106.7 degrees ), and not only 1 and 2, but also stibine 3 displayed a reversible redox wave in the cyclic voltammograms at very low potentials (1: 0.16 V, 2: 0.50 V, 3: 0.57 V vs Ag/Ag+), which suggests considerable stability of the corresponding cation radicals.     

Synthesis, structures, and emissive properties of platinum(II) complexes with a cyclometallating aryldiamine ligand

A new series of square planar Pt(II) complexes with the mer-coordinating tridentate ligand, pip(2)NCN(-) (pip(2)NCNH = 1,3-bis(piperdylmethyl)benzene), has been prepared: Pt(pip(2)NCN)Cl (2), Pt(pip(2)NCN)Br (3), Pt(pip(2)NCN)I (4), and [Pt(pip(2)NCN)(CH(3)N=C(CH(3))(2))][CF(3)SO(3)] (5). The complexes have been fully characterized by (1)H NMR spectroscopy, elemental analysis, and UV-vis spectroscopy. The X-ray crystal structures of pip(2)NCNBr (1), 2, and 5 are reported. Compound 1: triclinic, P, a = 10.081(1) A, b = 10.153(2) A, c = 10.390(1) A, alpha = 66.05(1) degrees, beta = 79.07(1) degrees, gamma = 64.51(1) degrees, V = 877.1(2) A(3), Z = 2. Complex 2: triclinic, P, a = 9.897(2) A, b = 10.191(2) A, c = 19.174(4) A, alpha = 75.09(3) degrees, beta = 76.14(3) degrees, gamma = 71.00(3) degrees, V = 1741.2(6) A(3), Z = 4. Complex 5: triclinic, P, a = 10.709(2) A, b = 11.2321(10) A, c = 12.447(2) A, alpha = 110.509(8) degrees, beta = 112.417(10) degrees, gamma = 91.066(9) degrees, V = 1276.1(3) A(3), Z = 2. In 77 K 3:1 EtOH/MeOH glassy solution, these colorless complexes exhibit weak red-orange to red emissions originating from a lowest spin-forbidden ligand field excited state.     

Syntheses and Crystal Structures of （S）-Methyl 2-（4-R-phenylsulfonamido）-3-（1H-indol-3-yl）propanoate （R = H （1） and Cl （2））

The title compounds （S）-methyl-2-（4-R-phenylsulfonamido）-3-（1H-indol-3- yl）propanoate （R = H （1）, Cl （2）） have been synthesized and their crystal structures also have been determined by X-ray single-crystal diffraction. Compound 1 （C18H18N2O4S） belongs to orthorhombic, space group P212121 with a = 9.6348（14）, b = 11.1517（17）, c = 16.412（3） A, V = 1763.4（5） A^3, Mr = 358.40, Z = 4, De = 1.350 g/cm^3,/t = 0.209 mm^-1, F（000） = 752, R = 0.0348 and wR = 0.0714. Compound 2 （CI8H17ClN2O4S） crystallizes in orthorhombic, space group P212121 with a = 9.3128（14）, b = 10.9655（16）, c = 17.783（3） A, V = 1815.9（5） A^3, Mr = 392.85, Z = 4, De = 1.437 g/cm^3, p = 0.352 mm^-1, F（000） = 816, R = 0.0389 and wR = 0.0845. The absolute structure Flack parameters X of compounds 1 and 2 are -0.03（8） and -0.06（7）, respectively. X-ray analysis reveals that the crystal structures of these two compounds both involve two intermolecular N-H…O hydrogen bond＇s.     

Ion-Bearing Propellers: Alkali Metal Complexes of Tris(2-alkoxyphenyl)amine Ionophores

NMR spectroscopic studies reveal that binding of Na(+) by tris(2-methoxyphenyl)amine (3) brings two of these tripod ethers together about the metal ion; the related double-tripod-ether ionophore 1,2-bis[2-(bis(2-methoxyphenyl)amino)phenoxy]ethane (4), in which two triarylamines are covalently attached, binds LiI, LiBPh(4), NaI, NaBPh(4), and KB(4-ClPh)(4). Dynamic NMR puts lower limits on binding free energies of 4 for Na(+) (71.8 kJ mol(-)(1)) and K(+) (66.8 kJ mol(-)(1)) ions. X-ray studies of 3(2).NaBPh(4), 4.NaBPh(4), 4.NaB(4-ClPh)(4), and 4.KB(4-ClPh)(4).CH(3)NO(2) show eight-coordinate M(+) ions bound between crystallographically independent, homochiral triarylamine tripod ethers in structures reminiscent of alkali metal [2.2.2] cryptates. Complexes crystallize as follows: 3(2).NaBPh(4), monoclinic, P2(1)/c, Z = 4, a = 10.701(3) ?, b = 37.593(3) ?, c = 13.774(2) ?, and beta = 98.24(2) degrees; 4.NaBPh(4), triclinic, P&onemacr;, Z = 2, a = 12.157(1) ?, b = 14.811(1) ?, c = 15.860(2) ?, alpha = 105.400(8) degrees, beta = 91.594(9) degrees, and gamma = 95.354(8) degrees; 4.NaB(4-ClPh)(4), monoclinic, P2(1)/n, Z = 4, a = 13.652(5) ?, b = 18.75(1) ?, c = 22.805(5) ?, and beta = 92.21(5) degrees; 4.KB(4-ClPh)(4).CH(3)NO(2), monoclinic, Pn, Z = 2, a = 13.663(4) ?, b = 12.228(3) ?, c = 18.712(8) ?, and beta = 91.45(3) degrees. They show variable N-M-N angles; 3(2).NaBPh(4) is surprisingly bent ( angleN-Na-N = 154.5 degrees ), while the 4.M(+) complexes are normal: nearly linear for Na(+) ( angleN-Na-N = 178.6, 178.1 degrees ) and again bent with the larger K(+) ( angleN-K-N = 164.5 degrees ). Finally, free 4 is structurally similar to 3; it crystallizes in the triclinic space group P&onemacr;, with Z = 2, a = 8.068(1) ?, b = 14.599(2) ?, c = 16.475(3) ?, alpha = 115.43(1) degrees, beta = 92.51(1) degrees, and gamma = 90.40(1) degrees.     

Synthesis and structural characterization of trinuclear Cu(II)-pyrazolato complexes containing mu(3)-OH, mu(3)-O, and mu(3)-Cl ligands. Magnetic susceptibility study of [PPN](2)[(mu(3)-O)Cu(3)(mu-pz)(3)Cl(3)

The nine-membered [-Cu(II)-N-N-](3) ring of trimeric copper-pyrazolato complexes provides a sturdy framework on which water is twice deprotonated in consecutive steps, forming mu(3)-OH and mu(3)-O species. In the presence of excess chlorides the mu(3)-O(H) ligand is replaced by two mu(3)-Cl ions. The interconversion of mu(3)-OH and mu(3)-O and the exchange of mu(3)-O(H) and mu(3)-Cl are reversible, and the three species involved have been structurally characterized: [PPN][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)(thf)].CH(2)Cl(2) (1a), monoclinic P2(1)/n, a = 10.055(2) A, b = 35.428(5) A, c = 15.153(2) A, beta = 93.802(3) degrees, V = 5386(1) A(3), Z = 4; [Bu(4)N][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)] (1b), triclinic P-1, a = 9.135(2) A, b = 13.631(2) A, c = 14.510(2) A, alpha = 67.393(2) degrees, beta = 87.979(2) degrees, gamma = 80.268(3) degrees, V = 1643.2(4) A(3), Z = 2; [PPN](2)[Cu(3)(mu(3)-O)(mu-pz)(3)Cl(3)] (2), monoclinic P2/c, a = 12.807(2) A, b = 13.093(2) A, c = 23.139(4) A, beta = 105.391(3) degrees, V = 3741(1) A(3), Z = 2; [PPN](2)[Cu(3)(mu(3)-Cl)(2)(mu-pz)(3)Cl(3)].0.75H(2)O.0.5CH(2)Cl(2) (3a), triclinic P-1, a = 14.042(2) A, b = 23.978(4) A, c = 25.195(4) A, alpha = 76.796(3) degrees, beta = 79.506(3) degrees, gamma = 77.629(3) degrees, V = 7988(2) A(3), Z = 4; [Bu(4)N](2)[Cu(3)(mu(3)-Cl)(2)(mu-pz)(3)Cl(3)] (3b), monoclinic C2/c, a = 17.220(2) A, b = 15.606(2) A, c = 20.133(2) A, beta = 103.057(2) degrees, V = 5270(1) A(3), Z = 4; [Et(3)NH][Cu(3)(mu(3)-OH)(mu-pz)(3)Cl(3)(pzH)] (4), triclinic P-1, a = 11.498(2) A, b = 11.499(2) A, c = 12.186(2) A, alpha = 66.475(3) degrees, beta = 64.279(3) degrees, gamma = 80.183(3) degrees, V = 1331.0(5) A(3), Z = 2. Magnetic susceptibility measurements show that the three copper centers of 2 are strongly antiferromagnetically coupled with J(Cu-Cu) = -500 cm(-1).     

Syntheses,structures, and properties of the bis(cyclopentadienyl) rare-earth imidodiphosphinochalocogenido compounds Cp2Ln[N(QPPh2)2] (Ln = La,Gd, Er,or Yb for Q = Se; Ln = Yb for Q = S)

The compounds Cp2Ln[N(QPPh2)2] (Ln = La (1), Gd (2), Er (3), or Yb (4) for Q = Se, Ln = Yb (5) for Q = S) have been synthesized from the corresponding rare-earth tris(cyclopentadienyl) compound and H[N(QPPh2)2]. The structures of compounds 1, 2, 3, and 5, as determined by X-ray crystallography, consist of a Cp2Ln fragment, coordinated eta 3 through two chalcogen atoms and an N atom of the imidodiphosphinochalcogenido ligand [N(QPPh2)2]-. In compound 4, the Cp2Yb moiety is coordinated eta 2 through the two Se atoms of the [N(SePPh2)2]-ligand. 31P and 77Se (for 1) NMR spectroscopies lend insight into the solution nature of these species. Crystal data: 1, C34H30LaNP2Se2, triclinic, P1, a = 9.7959(10) A, b = 12.4134(13) A, c = 13.9077(14) A, alpha = 88.106(2) degrees, beta = 88.327(2) degrees, gamma = 68.481(2) degrees, V = 1572.2(3) A3, T = 153 K, Z = 2, and R1(F) = 0.0257 for the 5947 reflections with I > .2 sigma(I); 2, C34H30GdNP2Se2, triclinic, P1, a = 9.7130(14) A, b = 12.2659(17) A, c = 13.953(2) A, alpha = 88.062(2) degrees, beta = 87.613(2) degrees, gamma = 69.041(2) degrees, V = 1550.7(4) A3, T = 153 K, Z = 2, and R1(F) = 0.0323 for the 5064 reflections with I > 2 sigma(I); 3, C34H30ErNP2Se2, triclinic, P1, a = 9.704(2) A, b = 12.222(3) A, c = 13.980(4) A, alpha = 88.230(4) degrees, beta = 87.487(4) degees, gamma = 69.107(4) degrees, V = 1547.4(7) A3, T = 153 K, Z = 2, and R1(F) = 0.0278 for the 6377 reflections with I > 2 sigma(I); 4, C34H30NP2Se2Yb.C4H8O, triclinic, P1, a = 12.087(4) A, b = 12.429(4) A, c = 23.990(7) A, alpha = 89.406(5) degrees, beta = 86.368(5) degrees, gamma = 81.664(5) degrees, V = 3558.8(18) A3, T = 153 K, Z = 4, and R1(F) = 0.0321 for the 11,883 reflections with I > 2 sigma(I); and 5, C34H30NP2S2Yb, monoclinic, P21/n, a = 13.8799(18) A, b = 12.6747(16) A, c = 17.180(2) A, beta = 91.102(3) degrees, V = 3021.8(7) A3, T = 153 K, Z = 4, and R1(F) = 0.0218 for the 6698 reflections with I > 2 sigma(I).