Halide Effects in the Formation of Four-Coordinate, Cationic Aluminum

This work was conducted as part of a broad-based effort to determine the factors that affect cation formation for organometallic aluminum complexes. In this study the adduct species R(2)AlX.NH(2)(t)Bu (R, X: Me, F (1); Me, Cl (2); Et, Cl (3); Me, Br (4)) and cationic complexes [R(2)Al(NH(2)(t)Bu)(2)]X (R, X: Me, Br (5); Et, Br (6); Me, I (7)) were examined. These complexes demonstrate that the reaction of R(2)AlX with excess NH(2)(t)Bu produces cationic complexes only when X = Br or I. All of the compounds were characterized by melting points, (1)H NMR, IR, elemental analyses, and, in some cases, X-ray crystallography. X-ray data: 2, triclinic, P&onemacr;, a = 6.277(3) ?, b = 8.990(3) ?, c = 10.393(3) ?, alpha = 71.97(1) degrees, beta = 80.25(3) degrees, gamma = 81.97(3) degrees, V = 547.0(4) ?(3), Z = 2, 1032 reflections with F > 4.0 sigma(F), R = 0.0520; 5, monoclinic, P2(1)/c, a = 9.099(1) ?, b = 10.292(1) ?, c = 17.255(2) ?, beta = 104.81(1) degrees, V = 1562.1(3) ?(3), Z = 4, 1464 reflections with F > 4.0 sigmaF, R = 0.0387; 6, monoclinic, P2(1)/c, a = 14.122(2) ?, b = 13.539(2) ?, c = 21.089(2) ?, beta = 107.73(1) degrees, V = 3841.2(9) ?(3), Z = 4, 781 reflections with F > 5.0 sigmaF, R = 0.0873; 7, monoclinic, P2(1)/n, a = 9.071(1) ?, b = 10.529(1) ?, c = 17.714(2) ?, beta = 103.67(1) degrees, V = 1644.0(3) ?(3), Z = 4, 1723 reflections with F > 4.0 sigmaF, R = 0.0451.     

Syntheses and Structural Characterization of Tetrahedral Four-Coordinate Gold(I) Complexes of 1,3,5-Triaza-7-phosphaadamantane. An Example of a Hydrogen-Bond-Directed Supramolecular Assembly

The synthesis and structural characterization of water-soluble four-coordinate gold(I) complexes containing monodentate phosphine ligands are described. The ligands used are 1,3,5-triaza-7-phosphaadamantane (TPA) and its protonated and methylated derivatives, [HTPA]Cl and [MeTPA]I. Formation of the four-coordinate gold(I) species is favored by the small cone angle of the phosphine (102 degrees ) and its ability to form a hydrogen-bonded network between the nitrogen atoms of the ligand and solvent water molecules. The gold center in all four complexes has a nearly regular tetrahedral geometry with an average P-Au-P angle of 109.5 degrees. [(HTPA)(3)(TPA)Au](PF(6))(4).4H(2)O.CH(3)CN(1) crystallizes in the monoclinic space group P2(1)/c (No. 14) with cell constants a = 20.719(3) ?, b = 15.606(2) ?, c = 17.854(2) ?, beta = 114.03(1) degrees, and Z = 4. Refinement of 4977 reflections and 650 parameters yields R = 0.0396 and R(w) = 0.0500. [(TPA)(4)Au]PF(6).1.5HCl.H(2)O (2), crystallizes in the monoclinic space group C2/c (No. 15) with cell constants a = 33.036(7) ?, b = 11.212(2) ?, c = 31.503(5) ?, b = 137.58(1) degrees, and Z = 8. Refinement of 3835 reflections and 470 parameters yields R = 0.0351 and R(w) = 0.0403. [(TPA)(4)Au]Cl(4).6H(2)O (3) was characterized structurally in the cubic space group Fd&thremacr;m (No. 227) with cell constants a = b = c = 20.020(2) ? and Z = 8. Refinement of 290 reflections and 28 parameters yields R = 0.0624 and R(w) = 0.1291. [(MeTPA)(4)Au](PF(6))(5).2CH(3)CN (4) crystallizes in the monoclinic space group C2/c (No. 15) with cell constants a = 23.337(3) ?, b = 14.855(3) ?, c = 35.317(5) ?, b = 97.95(1) degrees, and Z = 8. Refinement of 7840 reflections and 621 parameters yields R = 0.0493 and R(w) = 0.0698.     

Chemical and Biological Studies of Dichloro(2-((dimethylamino)methyl)phenyl)gold(III)

Several new organogold(III) derivatives of the type [AuX(2)(damp)] (damp = o-C(6)H(4)CH(2)NMe(2)) have been prepared [X = CN, SCN, dtc, or X(2) = tm; dtc = R(2)NCS(2) (R = Me (dmtc) or Et (detc)); tm = SCH(CO(2))CH(2)CO(2)Na] together with [AuCl(tpca)(damp)]Cl (tpca = o-Ph(2)PC(6)H(4)CO(2)H), [Au(dtc)(damp)]Y (Y = Cl, BPh(4)) and K[Au(CN)(3)(damp)]. The (13)C NMR spectra of these and previous derivatives have been fully assigned. In [Au(dtc)(2)(damp)] and K[Au(CN)(3)(damp)], the damp ligand is coordinated only through carbon, as shown by X-ray crystallography and/or NMR. [Au(detc)(2)(damp)] has space group C2/c, with a = 29.884(4) ?, b = 13.446(2) ?, c = 12.401(2) ?, beta = 99.45(3)(o), V = 4915 ?(3), Z = 8, and R = 0.057 for 1918 reflections. The damp and one detc ligand are monodentate, the other detc is bidentate; in solution, the complex shows dynamic behavior, with the detc ligands appearing equivalent. The crystal structure of [Au(dmtc)(damp)]BPh(4) [Pna2(1), a = 26.149(5) ?, b = 11.250(2) ?, c = 11.921(2) ?, V = 3507 ?(3), Z = 4, R = 0.073, 1772 reflections] shows both ligands to be bidentate in the cation, but the two Au-S distances are nonequivalent. The crystal structure of [Au(tm)(damp)] has also been determined [P2(1)/n, a = 18.267(7) ?, b = 9.618(3) ?, c = 18.938(4) ?, beta = 113.45(3)(o), V = 3053 ?(3), Z = 8, R = 0.079, 1389 reflections]. The tm is bound through sulfur and the carboxyl group which allows five-membered ring formation. In all three structures, the trans-influence of the sigma-bonded aryl group is apparent. [AuCl(2)(damp)] has been tested in vitroagainst a range of microbial strains and several human tumor lines, where it displays differential cytotoxicity similar to that of cisplatin. Against the ZR-75-1 human tumor xenograft, both [AuCl(2)(damp)] and cisplatin showed limited activity.     

Linear Trinuclear Pt.Mo-Mo Complexes [Mo(2)PtX(2)(pyphos)(2)(O(2)CR)(2)](2) (X = Cl, Br, I; R = CH(3), C(CH(3))(3); pyphos = 6-(Diphenylphosphino)-2-pyridonate) with an Axial Interaction between the Quadruply Bonded Mo(2) Moiety and the Platinum Atom

An example of a direct axial interaction of a platinum(II) atom with a Mo(2) core through a uniquely designed tridentate ligand 6-(diphenylphosphino)-2-pyridonate (abbreviated as pyphos) is described. Treatment of PtX(2)(pyphosH)(2) (2a, X = Cl; 2b, X = Br; 2c, X = I) with a 1:1 mixture of Mo(2)(O(2)CCH(3))(4) and [Mo(2)(O(2)CCH(3))(2)(NCCH(3))(6)](2+) (3a) in dichloromethane afforded the linear trinuclear complexes [Mo(2)PtX(2)(pyphos)(2)(O(2)CCH(3))(2)](2) (4a, X = Cl; 4b, X = Br; 4c, X = I). The reaction of [Mo(2)(O(2)CCMe(3))(2)(NCCH(3))(4)](2+) (3b) with 2a-c in dichloromethane afforded the corresponding pivalato complexes [Mo(2)PtX(2)(pyphos)(2)(O(2)CCMe(3))(2)](2) (5a, X = Cl; 5b, X = Br; 5c, X = I), whose bonding nature is discussed on the basis of the data from Raman and electronic spectra as well as cyclic voltammograms. The linear trinuclear structures in 4b and 5a-c were confirmed by NMR studies and X-ray analyses: 4b, monoclinic, space group C2/c, a = 34.733(4) ?, b = 17.81(1) ?, c = 22.530(5) ?, beta = 124.444(8) degrees, V = 11498(5) ?(3), Z = 8, R = 0.060 for 8659 reflections with I > 3sigma(I) and 588 parameters; 5a, triclinic, space group P&onemacr;, a = 13.541(3) ?, b = 17.029(3) ?, c = 12.896(3) ?, alpha = 101.20(2) degrees, beta = 117.00(1) degrees, gamma = 85.47(2) degrees, V = 2599(1) ?(3), Z = 2, R = 0.050 for 8148 reflections with I > 3sigma(I) and 604 parameters; 5b, triclinic, space group P&onemacr;, a = 12.211(2) ?, b = 20.859(3) ?, c = 10.478(2) ?, alpha = 98.88(1) degrees, beta = 112.55(2) degrees, gamma = 84.56(1) degrees, V = 2433.3(8) ?(3), Z = 2, R = 0.042 for 8935 reflections with I > 3sigma(I) and 560 parameters; 5c, monoclinic, space group P2(1)/n, a = 13.359(4) ?, b = 19.686(3) ?, c = 20.392(4) ?, beta = 107.92(2) degrees, V = 5101(2) ?(3), Z = 4, R = 0.039 for 8432 reflections with I > 3sigma(I) and 560 parameters.     

Optical and ODMR Studies of Luminescent Halo(dimethylphenylphosphine)gold(I) Crystals

Crystals of {(Me(2)PhP)AuX}(n) (Me = methyl; Ph = phenyl; X = Cl, Br, I; n = 2, 3) show emission from two excited states. Both states are assigned a triplet multiplicity, on the basis of their lifetimes and zero-field splittings. The structured, higher energy emission originates at approximately 360 nm and has the greater relative intensity at low temperatures. It is assigned as intraligand phosphorescence from a phenyl-localized (3)pipi state. The unstructured, lower energy emission has a peak wavelength that varies in the range 630-730 nm. It is assigned as phosphorescence from the triplet state due to the gold-based sigma(p) <-- sigma(s,d) excitation. The corresponding singlet state is observed at 290-310 nm. The results of SCF-Xalpha-SW calculations on the model complexes H(3)PAuX and (H(3)PAuX)(2) are also presented.     

Utility of Arylamido Ligands in Yttrium and Lanthanide Chemistry(1)

The reactivity of KNHAr reagents (Ar = C(6)H(5), C(6)H(3)Me(2)-2,6, C(6)H(3)(i)Pr(2)-2,6) with lanthanide and yttrium trichlorides has been investigated. With the larger metals Nd and Sm and the smaller 2,6-dimethyl-substituted ligand, the bimetallic dianionic complexes [K(THF)(6)](2)[Ln(&mgr;-NHC(6)H(3)Me(2)-2,6)(NHC(6)H(3)Me(2)-2,6)(3)](2) (Ln: Sm, 1a; Nd, 1b) are isolated as the potassium salts. Under the same reaction conditions YCl(3) forms a bimetallic anion which retains chloride: [K(DME)(2)(THF)(3)][Y(2)(&mgr;-NHC(6)H(3)Me(2)-2,6)(2)(&mgr;-Cl)(NHC(6)H(3)Me(2)-2,6)(4)(THF)(2)], 2. With the larger 2,6-diisopropyl ligands, neutral complexes are isolated in both solvated monometallic and unsolvated bimetallic forms. With Nd, a distorted octahedral trisolvate, Nd(NHC(6)H(3)(i)Pr(2)-2,6)(3)(THF)(3), 3, was obtained, whereas with Yb and Y the trigonal bipyramidal disolvates, Ln(NHC(6)H(3)(i)Pr(2)-2,6)(3)(THF)(2) (Ln: Yb, 4a; Y, 4b), were isolated. THF-free complexes of the NHC(6)H(3)(i)Pr(2)-2,6 ligand are available by reacting the amine NH(2)C(6)H(3)(i)Pr(2)-2,6 with Ln[N(SiMe(3))(2)](3) complexes. By this route, the dimers [Ln(&mgr;-NHC(6)H(3)(i)Pr(2)-2,6)(NHC(6)H(3)(i)Pr(2)-2,6)(2)](2) (Ln: Yb, 5a; Y, 5b) were isolated. The reaction of the unsubstituted arylamido salt KNHC(6)H(5) with NdCl(3) produced an insoluble material which was characterized as [Nd(NHC(6)H(5))(3)(KCl)(3)], 6. 6 reacted with Al(2)Me(6) in hexanes and produced a heteroleptic mixed-metal complex {[Me(2)Al(&mgr;-Me(2))](2)Nd(&mgr;(3)-NC(6)H(5))(&mgr;-Me)AlMe}(2), 7, and the trimeric aluminum arylamido complex [Me(2)Al(&mgr;-NHC(6)H(5))](3), 8. The solvent of crystallization and relevant crystallographic data for the compounds identified by X-ray analysis follow: 1a,THF, 156 K, P2(1)/n, a = 12.985(2) ?, b = 27.122(5) ?, c = 17.935(3) ?, beta = 100.19(1) degrees, V = 6216(1) ?(3), Z = 2, 6148 reflections (I > 3sigma(I)), R(F)() = 7.1%; 1b,THF, 156 K, P2(1)/n, a = 12.998(2) ?, b = 27.058(3) ?, c = 17.962(2) ?, beta = 99.74(1) degrees, V = 6225(1) ?(3), Z = 2; 2,DME/hexanes, P2(1)/n, a = 23.335(2) ?, b = 12.649(1) ?, c = 27.175(3) ?, beta = 96.36(1) degrees, V = 7971(1) ?(3), Z = 4, 2788 reflections (I > 3sigma(I)), R(F)() = 9.5%; 3, THF, P2(1), a = 12.898(1) ?, b = 16.945(1) ?, c = 13.290(1) ?, beta = 118.64(2) degrees, V = 2549.3(3) ?(3), Z = 2, 3414 reflections (I > 3sigma(I)), R(F)() = 4.3%; 4a, hexanes, P2(1), a = 9.718(2) ?, b = 19.119(3) ?, c = 12.640(2) ?, beta = 112.08(1) degrees, V = 2176.3(6) ?(3), Z = 2, 2933 reflections (I > 3sigma(I)), R(F)() = 4.3%; 4b, hexanes, 158 K, a = 9.729(2) ?, b = 19.095(5) ?, c = 12.744(1) ?, beta = 112.11(1) degrees, V = 2193.4(6) ?(3); 5b, hot toluene, 158 K, P2(1), a =19.218(9) ?, b = 9.375(3) ?, c = 19.820(5) ?, beta = 110.25(2) degrees, V = 3350(2)?(3), Z = 2, 1718 reflections (I > 2sigma (I)), R1 = 9.7%; 7, hexanes, 156 K, P&onemacr;, a = 9.618(3) ?, b = 12.738(4) ?, c = 9.608(3) ?, alpha = 99.32(1) degrees, beta = 108.87(1) degrees, gamma = 94.23(1) degrees, V = 1089.1(6) ?(3), Z = 2, 2976 reflections (I > 3sigma(I)), R(F)() = 3.9%; 8, hexanes, 156 K, Pcab, a = 23.510(5) ?, b = 25.462(5) ?, c = 8.668(2) ?, V = 5188(1) ?(3), Z = 8, 1386 reflections (I > 3sigma(I)), R(F)() = 5.7%.     

Structural and Spectroscopic Characterization of Iron(III) Dioxoporphodimethene Complexes and Their Autoreduction to an Iron(II) Complex in Pyridine

Three iron complexes of the meso-dioxo derivative of octaethylporphryin (trans-H(2)OEPO(2)) were characterized by X-ray diffraction. Green ClFe(III)(trans-OEPO(2)).1.5C(6)H(6) crystallizes in the monoclinic space group P2(1)/c with a = 13.766(3) ?, b = 19.075(3) ?, c = 15.217(3) ?, beta = 99.87(2) degrees at 123 K with Z = 4. Refinement of 2712 reflections with F > 6.0sigma(F) and 223 parameters yielded R = 0.0624, R(w) = 0.0596. The iron complex contains a domed dioxoporphodimethene macrocyclic ligand. The observation of a five-coordinate iron(III) ion with an axial Fe-Cl distance of 2.232(2) ? and in-plane Fe-N distances averaging 2.082 ? is consistent with its high-spin (S = (5)/(2)) character. This monomer is readily converted to the green {Fe(III)(trans-OEPO(2))}(2)O using aqueous hydroxide. {Fe(III)(trans-OEPO(2))}(2)O crystallizes in the monoclinic space group C2/c with a = 23.541(8) ?, b = 15.392(5) ?, c = 18.686(8) ?, and beta = 90.09(3) degrees at 294 K with Z = 8. Refinement of 3472 reflections with F > 6.0sigma(F) and 393 parameters yielded R = 0.0484, R(w) = 0.0527. The complex possesses a crystallographically imposed 2-fold symmetry axis that passes through the oxo ligand. The dioxoporphodimethene ligands within the molecule are roof-shaped and fold away from each other. The axial Fe-O distance is 1.749(1) ? with longer in-plane Fe-N distances (average 2.077 ?). The Fe-O-Fe angle of 165.4(2) degrees deviates significantly from linearity and is more acute than related porphyrin complexes. Pyridine solutions of either the iron(III) monomer or &mgr;-oxo dimer autoreduce over a period of days to give (py)(2)Fe(II)(trans-OEPO(2)). This red compound crystallizes in the space group P2(1) with a = 19.177(4) ?, b = 20.039(4) ?, c = 10.547(2) ?, and beta = 100.36(3) degrees at 130 K with Z = 2. Refinement of 5090 reflections with one restraint and 984 parameters yielded R1 = 0.0684, wR2 = 0.1763. The complex crystallizes with two distinct molecules in the asymmetric unit; each molecule contains a different degree of disorder with respect to the trans meso oxygen atoms (50/50, 71/29). Each independent molecule exhibits severe ruffling of the macrocycle. The six coordinate iron(II) center is diamagnetic. The axial Fe-N(pyridine) distances average 1.98 ?, and the in-plane Fe-N(pyrrole) distances average 1.95 ?. A common trend observed for the dioxoporphodimethene macrocycle in all of these structures is an elongation toward the trans oxidized meso carbons. These complexes were originally prepared as cis and trans isomeric mixtures that can be enriched in the trans isomer by fractional crystallization. This is evident in their distinctive (1)H NMR spectra. In addition, these compounds are characterized by electron impact mass spectrometry and UV-visible, ESR, and infrared spectroscopies.     

Stereochemical Consequences of the Bismuth Atom Electron Lone Pair, a Comparison between MX(6)E and MX(6) Systems. Crystal and Molecular Structures of Tris[N-(P,P-diphenylphosphinoyl)-P,P-diphenylphosphinimidato]bismuth(III), [Bi{(OPPh(2))(2)N}(3)], -indium(III), [In{(OPPh(2))(2)N}(3)].C(6)H(6), and -gallium(III), [Ga{(OPPh(2))(2)N}(3)].CH(2)Cl(2)

The tetraphenylimidodiphosphinate [N-(P,P-diphenylphosphinoyl)-P,P-diphenylphosphinimidate] ion forms stable tris-chelates with the Bi(III), In(III), and Ga(III) cations. The crystal and molecular structures of [M{(OPPh(2))(2)N}(3)] (M = Ga, In, Bi) were determined by X-ray diffractometry. The geometry around the bismuth atom in compound 3 displays an approximately C(3)(v)() symmetry. This arrangement suggests the presence of a stereoactive lone pair of electrons, which is located in one of the triangular octahedral faces. Derivative 3 crystallizes in the triclinic space group P&onemacr; with Z = 2, a = 14.006(6) ?, b = 14.185(4) ?, c = 17.609(8) ?, alpha = 88.45(2) degrees, beta = 79.34(2) degrees, and gamma = 78.23(2) degrees. The structures of the gallium(III) and indium(III) tris-chelate oxygen-based complexes (1 and 2, respectively) were compared with the bismuth analogue in order to determine the ligand steric bulk influence on the coordination sphere in the absence of the electron lone pair. Complex 1 crystallizes as the [Ga{(OPPh(2))(2)N}(3)].CH(2)Cl(2) solvate in the triclinic space group P&onemacr;; Z = 2, a = 13.534(4) ?, b = 13.855(4) ?, c = 18.732(7) ?, alpha = 95.48(2) degrees, beta = 98.26(2) degrees, and gamma = 97.84(2) degrees. Crystal data for the benzene solvate of 2, [In{(OPPh(2))(2)N}(3)].C(6)H(6): triclinic space group P&onemacr;, Z = 2, a = 13.542(9) ?, b = 15.622(3) ?, c = 18.063(5) ?, alpha = 98.21(1) degrees, beta = 104.77(0) degrees, and gamma = 92.260(0) degrees.     

Imide Transfer Properties and Reactions of the Magnesium Imide ((THF)MgNPh)(6): A Versatile Synthetic Reagent

Imide transfer properties of ((THF)MgNPh)(6) (1) and the synthesis of the related species {(THF)MgN(1-naphthyl)}(6).2.25THF (2), via the reaction of dibutylmagnesium with H(2)N(1-naphthyl), in a THF/heptane mixture are described. Treatment of 1 with Ph(2)CO, 4-Me(2)NC(6)H(4)NO, t-BuNBr(2) (3), PCl(3), or MesPCl(2) (Mes = 2,4,6-Me(3)C(6)H(2)-) leads to the isolation of Ph(2)CNPh (4), 4-Me(2)NC(6)H(4)NNPh (5), t-BuNNPh (6), (PhNPCl)(2) (7), or (MesPNPh)(2) (8) in moderate yield. Reaction between 1 and GeCl(2).dioxane, SnCl(2), or PbCl(2) affords the M(4)N(4) (M = Ge, Sn, Pb) cubane imide derivative (GeNPh)(4) (9), [(SnNPh)(4).{MgCl(2)(THF)(4)}](infinity) (10), (SnNPh)(4).0.5PhMe (11), or (PbNPh)(4).0.5PhMe (12). Interaction of 1 with Ph(3)PO, (Me(2)N)(3)PO, or Ph(2)SO furnishes the complex (Ph(3)POMgNPh)(6) (13), {(Me(2)N)(3)POMgNPh}(6).2PhMe (14), or (Ph(2)SOMgNPh)(6) (15). The addition of 3 equiv of MgBr(2) to 1 gives 1.5 equiv of ((THF)Mg)(6)(NPh)(4)Br(4) (16) in quantitative yield, whereas treatment of 16 with 4 equiv of 1,4-dioxane is an alternative synthetic route to 1. Compounds 2, 3, 9, 10, and 14 were characterized by X-ray crystallography. The reactions demonstrate that 1 is a versatile and useful reagent for the synthesis of a variety of main group imides. Crystal data at 130 K with Mo Kalpha (lambda = 0.710 73 ?) radiation for 3 or Cu Kalpha (lambda = 1.541 78 ?) radiation for 2, 9, 10, and 14: 2, C(93)H(108)Mg(6)N(6)O(7.25), a = 28.101(7) ?, b = 35.851(7) ?, c = 36.816(7) ?, Z = 2, space group Fddd, R = 0.068 for 3500 (I > 2sigma(I)) data; 3, C(4)H(9)Br(2)N, a = 6.682(2) ?, b = 10.834(3) ?, c = 11.080(3) ?, alpha = 66.25(2) degrees, beta = 89.88(2) degrees, gamma = 82.53(2) degrees, Z = 4, space group P&onemacr;, R = 0.038 for 2043 (I > 2sigma(I)) data; 9, C(24)H(20)Ge(4)N(4), a = 10.749(2) ?, b = 12.358(3) ?, c = 35.818(7) ?, Z = 8, space group Pbca, R = 0.040 for 2981 (I > 2sigma(I)) data; 10, C(40)H(52)Cl(2)MgN(4)O(4)Sn(4), a = 12.770(3) ?, b = 13.554(3) ?, c = 25.839(5) ?, Z = 4, space group P2(1)2(1)2(1), R = 0.040 for (I > 2sigma(I)) data; 14, C(86)H(154)Mg(6)N(4)O(6)P(6), a = 22.478(4) ?, b = 16.339(3) ?, c = 29.387(6) ?, Z = 4, space group Pbcn, R = 0.081 for 4696 (I >2sigma(I)) data.     

Synthesis and Structural Characterization of [(η~5-C_5Me_5)_2Mo_2Fe_2S_4Br_2]

1 INTRODUCTION We once reported a CS bond cleavage reaction of (h5-C5Me5)Mo(StBu)3, which led to a Mo(IV) thio/thiolate complex (h5-C5Me5)MoS2(StBu)[1]. This reaction was facilitated by oxidants such as S8, gray selenium, and FeCl3[2]. The reaction with FeCl3 gave rise to a cubane cluster [(h5-C5Me5)2Mo2Fe2S4Cl2], which served as an excellent building block to construct various Mo/Fe/S clusters[2]. In this paper, we report the crystal structure of [(h5-C5Me5)2Mo2Fe…     

Perturbation of the Electronic Structure of a Copper(II) ion by a Cu(I)Cl Moiety in a Class I Mixed Valence Copper Complex, Cu(II)(Me(5)dien)Cl(2)(Cu(I)Cl)

A new mixed valence copper complex Cu(II)(Me(5)dien)Cl(2)(Cu(I)Cl) (2) was obtained from the reaction of CuCl with Cu(II)(Me(5)dien)Cl(2) (1) in acetonitrile. The structures of 1 and 2 have been determined by single-crystal X-ray diffraction analyses. Compound 1 crystallizes in the monoclinic space group P2(1)/n with a = 8.374(5) ?, b = 17.155(3) ?, c = 23.806(5) ?, beta = 94.40(4) degrees, Z = 8, and V = 3398(1) ?(3) while compound 2 crystallizes in orthorhombic space group Pbcn with a = 14.71(1) ?, b = 16.06(2) ?, c = 13.38(1) ?, Z = 8, and V = 3159(5) ?. The Cu(II)(Me(5)dien)Cl(2) unit in both compounds has a similar distorted square-pyramidal geometry. The Cu(I)Cl moiety in 2 is attached to the Cu(II) unit via two bridging chlorine atoms and has a distorted trigonal planar geometry. UV-vis and EPR spectroscopic studies and molecular orbital calculations established the presence of significant perturbation of the Cu(I)Cl unit to the electronic structure of the Cu(II) ion in compound 2.     

X-ray Crystallographic Study of the Ruthenium Blue Complexes [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O, [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, and [Ru(2)I(3)(tacn)(2)](PF(6))(2): Steric Interactions and the Ru-Ru "Bond Length"

X-ray crystal structures are reported for the following complexes: [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O (tacn = 1,4,7-triazacyclononane), monoclinic P2(1)/n, Z = 4, a = 14.418(8) ?, b = 11.577(3) ?, c = 18.471(1) ?, beta = 91.08(5) degrees, V = 3082 ?(3), R(R(w)) = 0.039 (0.043) using 4067 unique data with I > 2.5sigma(I) at 293 K; [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, monoclinic P2(1)/a, Z = 4, a = 13.638(4) ?, b = 12.283(4) ?, c = 18.679(6) ?, beta = 109.19(2) degrees, V = 3069.5 ?(3), R(R(w)) = 0.052 (0.054) using 3668 unique data with I > 2.5sigma(I) at 293 K; [Ru(2)I(3)(tacn)(2)](PF(6))(2), cubic P2(1)/3, Z = 3, a = 14.03(4) ?, beta = 90.0 degrees, V = 2763.1(1) ?(3), R (R(w)) = 0.022 (0.025) using 896 unique data with I > 2.5sigma(I) at 293 K. All of the cations have cofacial bioctahedral geometries, although [Ru(2)Cl(3)(tacn)(2)](PF(6))(2).4H(2)O, [Ru(2)Br(3)(tacn)(2)](PF(6))(2).2H(2)O, and [Ru(2)I(3)(tacn)(2)](PF(6))(2) are not isomorphous. Average bond lengths and angles for the cofacial bioctahedral cores, [N(3)Ru(&mgr;-X)(3)RuN(3)](2+), are compared to those for the analogous ammine complexes [Ru(2)Cl(3)(NH(3))(6)](BPh(4))(2) and [Ru(2)Br(3)(NH(3))(6)](ZnBr(4)). The Ru-Ru distances in the tacn complexes are longer than those in the equivalent ammine complexes, probably as a result of steric interactions.     

Developing Reagents To Orient Fullerene Derivatives. Formation and Structural Characterization of (eta(2)-C(60)O)Ir(CO)Cl(As(C(6)H(5))(3))(2)

In order to obtain crystals of fullerene oxides that are suitable for single-crystal X-ray diffraction, the reactions between C(60)O and Vaska type iridium complexes have been examined. While reaction with Ir(CO)Cl(P(C(6)H(5))(3))(2)(and with triphenylphosphine but not triphenylarsine) results in partial deoxygenation of the fullerene epoxide, reaction with Ir(CO)Cl(As(C(6)H(5))(3))(2)()()produces crystalline (eta(2)-C(60)O)Ir(CO)Cl(AsPh(3))(2).4.82C(6)H(6).0.18CHCl(3). Black triangular prisms of (eta(2)-C(60)O)Ir(CO)Cl(AsPh(3))(2).4.82C(6)H(6).0.18CHCl(3)form in the monoclinic space group P2(1)/n with a = 14.662(2) ?, b = 19.836(2) ?, c = 28.462(5) ?, and beta = 100.318(12) degrees at 123 (2) K with Z = 4. Refinement (on F(2)) of 10 472 reflections and 1095 parameters with 10 restraints yielded wR2 = 0.152 and a conventional R = 0.066 (for 7218 reflections with I > 2.0sigma(I)). The structure shows that the iridium complex is bound to a 6:6 ring junction of the fullerene with four partially occupied sites for the epoxide oxygen atom. Thus, while deoxygenation of the fullerene does not occur upon reaction with Ir(CO)Cl(AsPh(3))(2), there is a greater degree of disorder in (eta(2)-C(60)O)Ir(CO)Cl(AsPh(3))(2)than previously reported for (eta(2)-C(60)O)Ir(CO)Cl(PPh(3))(2).     

Synthesis and structural characterization of luminescent trinuclear gold(I) complexes with dithiocarbamates

We have synthesized a series of trinuclear gold(I) complexes, namely, [Au3(mu-dpmp)(S2CNR2)nCl3-n] (n = 0-3; R = Me, CH2Ph), [Au3(mu-dpmp)(mu-S2CNR2)Cl](CF3SO3) (R = Me, CH2Ph), and [Au3(mu-dpmp)(mu-S2CNMe2)(C6F5)]X (X = Cl, CF3SO3), containing the triphosphine dpmp [bis(diphenylphosphinomethyl)phenylphosphine] and varying amounts of dithiocarbamate. NMR experiments show fluxional behavior in solution for most of these derivatives because several arrangements of the ligands are possible. The crystal structure of [(mu-dpmp)(AuCl)3] has been determined by X-ray diffraction studies; the molecule displays mirror symmetry and involves an angular arrangement of the gold atoms [Au-Au-Au 119.603(14) degrees, Au-Au 3.3709(4) A]. We have studied the optical properties of these derivatives in the solid state, finding a red shift as a function of the dithiocarbamate number and, for some derivatives, wavelength-dependent emission spectra at low temperature.     

双羰基双膦合铂(O)配合物的合成及其与卤代烃的氧化加成反应

本文报道一种合成标题配合物Pt(diphos)(CO)2的简便方法及其与碳-卤键的氧化加成反应. 在一氧公碳气氛存在下用NaBH4还原[Pt(diphos)Cl2]可“原位"得到[Pt(diphos)(CO)2]的THF溶液, 能与卤代烃发生氧化加成反应, 并用^1H NMR和^3^1PNMR谱进行了研究. 氧化加成反应按自由基非链式机理进行, 加成产物[Pt(diphos)X2]之一[Pt(d(i-Pr)pe)I2]经过分子结构测定, 反应能力与卤代烃和双膦螯合配体的电子性质有关.     

Rational synthesis of [Ge9{Si(SiMe3)3}3]- from its parent Zintl ion Ge9(4-)

Reported is the first rational synthesis of a trisubstituted deltahedral Zintl ion, [Ge(9){Si(SiMe(3))(3)}(3)](-) in this case, by the addition of the three substituents in a reaction of the parent naked deltahedral Zintl ion Ge(9)(4-) with {(Me(3)Si)(3)Si}Cl. The new species were crystallized and structurally characterized in [K(2,2,2-crypt)](2)[Ge(9){Si(SiMe(3))(3)}(3)] (monoclinic, P2(1)/c, a = 26.497(3) ?, b = 24.090(2) ?, c = 29.268(3) ?, β = 113.888(2)°, V = 17082(3) ?(3), Z = 8, R1/wR2 = 0.0436/0.0812 for the observed data and 0.1023/0.1010 for all data).     

Syntheses and Crystal Structures of Two New Iron-sulfur Carbonyl Complexes: [Fe_2(SC_6H_4Cl)_2(CO)_6]·0.5(Et_2O) and [Fe_3(SC_6H_4NH_2)_6(CO)_6]·2(MeOH)

Two new iron-sulfur carbonyl complexes, [Fe2(SC6H4Cl)2(CO)6]?0.5(Et2O) 1 and [Fe3(SC6H4NH2)6(CO)6]?2(MeOH) 2, have been prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Crystal data for 1: monoclinic, C2/c, a = 18.4439(8), b = 11.0999(5), c = 25.1830(10) ?, β = 97.0370(10)o, V = 5116.8(4) ?3, Z = 8, C20H13Cl2Fe2O6.50S2, Mr = 604.02, Dc = 1.568 g/cm3, μ = 1.540 mm–1, F(000) = 2424, the final R = 0.0545 and wR = 0.1454 for 3443 observed reflections with I > 2σ(I); 2: monoclinic, P21/n, a = 12.350, b = 26.3050(11), c = 16.057 ?, β = 97.891(3)°, V = 5166.9(2) ?3, Z = 4, C44H44Fe3N6O8S6, Mr = 1144.76, Dc = 1.472 g/cm3, μ = 1.128 mm–1, F(000) = 2352, the final R = 0.0442 and wR = 0.1197 for 7978 observed reflections with I > 2σ(I). Complex 1 contains one iron dimer, in which two tricarbonyliron(I) fragments are bridged together by two 4-chlorophenylthiolate ligands, whereas complex 2 contains a linear tri-iron cluster, in which two terminal tricarbonyliron(II) fragments and the central Fe(II) atom are linked together by six 4-aminophenylthiolate bridging ligands.     

Thermal Coupling Reactions of 1-Phenyl-3,4-dimethylphosphole within the Coordination Sphere of Palladium(II)

The thermolyses of dihalobis(1-phenyl-3,4-dimethylphosphole)palladium(II) complexes [(DMPP)(2)PdX(2), X = Cl, Br, I] were investigated in 1,1,2,2-tetrachloroethane solutions at 145 degrees C and in the crystalline state at 140 degrees C. For cis-(DMPP)(2) PdCl(2) and cis- or trans-(DMPP)(2) PdBr(2) four types of products were formed: (1) [4 + 2] cycloaddition products, (2) [2 + 2] cycloaddition products, (3) compounds that result from 1,5-hydrogen migration from a methyl group on one phosphole to the beta-carbon of an adjacent phosphole (exo-methylene), and (4) products that result from an intermolecular [4 + 2] coupling of two phospholes followed sequentially by phosphinidene elimination and intramolecular [4 + 2] cycloaddition to another phosphole to give diphosphatetracyclotetradecatrienes (DPTCT). trans-(DMPP)(2)PdBr(2) undergoes thermal isomerization to cis-(DMPP)(2)PdBr(2) in the solid state, and cis- and trans-(DMPP)(2)PdBr(2) give the same products in both their solid- and solution-state thermolyses. In contrast, trans-(DMPP)(2) PdI(2) neither isomerizes to the cis-isomer nor undergoes any of the phosphole coupling reactions in either the solution or solid state. The crystal structures of trans-(DMPP)(2)PdX(2) (X = Br, I), {(DMPP)(2)[2 + 2]}PdBr(2), {(DMPP)(2)(exo-methylene)}PdBr(2), and (DPTCT)PdCl(2) were determined. They crystallize in the monoclinic P2(1)/c, triclinic P&onemacr;, monoclinic P2(1)/c, monoclinic P2(1)/n, and orthorhombic P2(1)2(1)2(1) space groups in units cells of the following dimensions: a = 10.158 (3) ?, b = 14.876 (4) ?, c = 16.829 (5) ?, beta = 104.25(2) degrees, rho(calc) = 1.732 g/cm(3), Z = 4; a = 9.025(1) ?, b = 11.023(1) ?, c = 13.833 (1) ?, alpha = 101.15(1) degrees, beta = 98.82(1) degrees, gamma = 105.30(1) degrees, rho(calc) = 1.886 g/cm(3), Z = 2; a = 13.090 (2) ?, b = 17.637 (2) ?, c = 21.834 (2) ?, beta = 100.51 (1) degrees, rho(calc) = 1.738 g/cm(3), Z = 4, a = 10.721 (1) ?, b = 16.929 (1) ?, c = 14.675(1) ?, beta = 97.86 (1) degrees, rho(calc) = 1.663 g/cm(3), Z = 4; and a = 15.532 (3) ?, b = 19.401 (4) ?, c = 9.910 (2) ?, rho(calc) = 1.490 g/cm(3), Z = 2, respectively. Least-squares refinements converged at final values of R(F) of 0.041, 0.0354, 0.0624, 0.0533, and 0.035 for 2770, 2672, 2729, 2159, and 2525 independent observed reflections, respectively. Kinetic studies suggest that the reaction mechanisms are the same in both the solid and solution states and that the reaction mechanisms are substantially different from those previously reported for the thermolyses of the analogous cis-(DMPP)(2)PtX(2) complexes.     

Synthesis and Crystal Structure of cis—[meso—1,3—Bis（propylsulfinyl）propane]dichloroplatinum（Ⅱ）

1 INTRODUCTION A number of Pt complexes with monosulfoxide have been isolated and characterized[1]. It was indicated that the sulfoxide group trends to coordinate to soft metals (Pt, Pd, etc.) by its sulfur atom[2]. Pt(Ⅱ) trends to bond to disulfoxides in cis-mode and such complexes have potential antitumor activity[2]. However, only few examples of such complexes have been structurally characterized[3]. We will report herein the crystal structure of a new Pt(Ⅱ) complex with a disulf…     

Reactions of the Dirhenium(II) Complexes Re(2)X(4)(dppm)(2) (X = Cl, Br; dppm = Ph(2)PCH(2)PPh(2)) with Isocyanides. 10.(1) Synthesis and Characterization of the Complex [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(2)(CNXyl)]O(3)SCF(3) and Several Isomeric Forms of [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)]Y (Y = PF(6), O(3)SCF(3))

The reactions of the unsymmetrical, coordinatively unsaturated dirhenium(II) complexes [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)]Y (XylNC = 2,6-dimethylphenyl isocyanide; Y = O(3)SCF(3) (3a), PF(6) (3b)) with XylNC afford at least three isomeric forms of the complex cation [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)](+). Two forms have very similar bis(&mgr;-halo)-bridged edge-sharing bioctahedral structures of the type [(CO)BrRe(&mgr;-Br)(2)(&mgr;-dppm)(2)Re(CNXyl)(2)]Y (Y = O(3)SCF(3) (4a/4a'), PF(6) (4b/4b')), while the third is an open bioctahedron [(XylNC)(2)BrRe(&mgr;-dppm)(2)ReBr(2)(CO)]Y (Y = O(3)SCF(3) (5a), PF(6) (5b)). While the analogous chloro complex cation [Re(2)Cl(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)](+) was previously shown to exist in three isomeric forms, only one of these has been found to be structurally similar to the bromo complexes (i.e. the isomer analogous to 5a and 5b). The reaction of 3a with CO gives the salt [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(2)(CNXyl)]O(3)SCF(3) (7), in which the edge-sharing bioctahedral cation [(XylNC)BrRe(&mgr;-Br)(&mgr;-CO)(&mgr;-dppm)(2)ReBr(CO)](+) has an all-cis arrangement of pi-acceptor ligands. The Re-Re distances in the structures of 4b', 5a, and 7 are 3.0456(8), 2.3792(7), and 2.5853(13) ?, respectively, and accord with formal Re-Re bond orders of 1, 3, and 2, respectively. Crystal data for [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)](PF(6))(0.78)(ReO(4))(0.22).CH(2)Cl(2) (4b') at 295 K: monoclinic space group P2(1)/n (No. 14) with a = 19.845(4) ?, b = 16.945(5) ?, c = 21.759(3) ?, beta = 105.856(13) degrees, V = 7038(5) ?(3), and Z = 4. The structure was refined to R = 0.060 (R(w) = 0.145) for 14 245 data (F(o)(2) > 2sigma(F(o)(2))). Crystal data for [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(CNXyl)(2)]O(3)SCF(3).C(6)H(6) (5a) at 173 K: monoclinic space group P2(1)/n (No. 14) with a = 14.785(3) ?, b = 15.289(4) ?, c = 32.067(5) ?, beta = 100.87(2) degrees, V=7118(5) ?(3), and Z = 4. The structure was refined to R = 0.046 (R(w) = 0.055) for 6962 data (I > 3.0sigma(I)). Crystal data for [Re(2)Br(3)(&mgr;-dppm)(2)(CO)(2)(CNXyl)]O(3)SCF(3).Me(2)CHC(O)Me (7) at 295 K: monoclinic space group P2(1)/n (No. 14) with a = 14.951(2) ?, b = 12.4180(19) ?, c = 40.600(5) ?, beta = 89.993(11) degrees, V = 7537(3) ?(3), and Z = 4. The structure was refined to R = 0.074 (R(w) = 0.088) for 6595 data (I > 3.0sigma(I)).