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Louise M. Liable-Sands

Publications and source records attributed to Louise M. Liable-Sands.

14 recordsLinked to original sources
PubMed1999

One-Dimensional Copper(I) Coordination Polymers Based on a Tridentate Thioether Ligand.

The one-dimensional copper(I) coordination polymers Cu(3){MeSi(CH(2)SMe)(3)}(2)X(3) (X = Cl, Br) and [{MeSi(CH(2)SMe)(3)}Cu(NCMe)]Y (Y = OSO(2)CF(3), BF(4), PF(6)) were readily obtained in very good to excellent yields (80-95%) by reacting CuX or [Cu(NCMe)(4)]Y, respectively, with the tridentate thioether ligand MeSi(CH(2)SMe)(3) in acetonitrile. The new complexes were characterized by a combination of analytical and spectroscopic techniques, including electrospray ionization mass spectrometry and, for the bromo and hexafluorophosphate derivatives, single-crystal X-ray diffraction. Both complexes exhibit one-dimensional chain structures with approximately tetrahedral copper centers and bridging unidentate/bidentate thioether ligands.

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PubMed1999

Synthesis, Structure, and Molecular Orbital Studies of Yttrium, Erbium, and Lutetium Complexes Bearing eta(2)-Pyrazolato Ligands: Development of a New Class of Precursors for Doping Semiconductors.

Treatment of yttrium metal with bis(pentafluorophenyl)mercury (1.5 equiv), 3,5-di-tert-butylpyrazole (3 equiv), and pyridine (2 equiv) in toluene at ambient temperature for 120 h afforded tris(3,5-di-tert-butylpyrazolato)bis(pyridine)yttrium(III) (33%). In an analogous procedure, the reaction of erbium metal with 3,5-dialkylpyrazole (alkyl = methyl or tert-butyl), bis(pentafluorophenyl)mercury, and a neutral nitrogen donor (4-tert-butylpyridine, pyridine, n-butylimidazole, or 3,5-di-tert-butylpyrazole) yielded tris(3,5-di-tert-butylpyrazolato)bis(4-tert-butylpyridine)erbium(III) (63%), tris(3,5-di-tert-butylpyrazolato)bis(pyridine)erbium(III) (88%), tris(3,5-di-tert-butylpyrazolato)bis(n-butylimidazole)erbium(III) (48%), tris(3,5-dimethylpyrazolato)bis(4-tert-butylpyridine)erbium(III) (50%), and tris(3,5-di-tert-butylpyrazolato)(3,5-di-tert-butylpyrazole)erbium(III) (59%), respectively. Treatment of tris(cyclopentadienyl)lutetium(III) or tris(cyclopentadienyl)erbium(III) with 3,5-di-tert-butylpyrazole (3 equiv) and 4-tert-butylpyridine (2 equiv) in toluene at ambient temperature for 24 h afforded tris(3,5-di-tert-butylpyrazolato)bis(4-tert-butylpyridine)lutetium(III) (83%) and tris(3,5-di-tert-butylpyrazolato)bis(4-tert-butylpyridine)erbium(III) (41%), respectively. The X-ray crystal structures of all new complexes were determined. The X-ray structure analyses revealed seven- and eight-coordinate lanthanide complexes with all-nitrogen coordination spheres and eta(2)-pyrazolato ligands. Molecular orbital calculations were carried out on dichloro(pyrazolato)diammineyttrium(III). The calculations demonstrate that eta(2)-bonding of the pyrazolato ligand is favored over the eta(1)-bonding mode and give insight into the bonding between yttrium and the pyrazolato ligands. Complexes bearing 3,5-di-tert-butylpyrazolato ligands can be obtained in a high state of purity and sublime without decomposition (150 degrees C, 0.1 mmHg). Application of these complexes as source compounds for chemical vapor deposition processes is discussed.

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PubMed1999

Tris[(alkylthio)methyl]silanes: Syntheses and Structures of Chromium, Molybdenum, and Tungsten Complexes with a Tripodal Thioether Ligand.

The first member of a new family of tripodal thioether ligands, the methyltris[(alkylthio)methyl]silanes MeSi(CH(2)SR)(3) (R = Me), has been synthesized and characterized. Reactivity studies lead to the isolation of the complete series of group 6 metal carbonyl derivatives {eta(3)-MeSi(CH(2)SMe)(3)}M(CO)(3) (M = Cr, Mo, W), whose structures have been determined by single-crystal X-ray diffraction. The three complexes are isomorphous and display distorted octahedral structures with face-capping tridentate thioether ligands. {eta(3)-MeSi(CH(2)SMe)(3)}Cr(CO)(3) is monoclinic, P2(1)/c, a = 8.1658(2) Å, b = 15.0563(2) Å, c = 26.5791(3) Å, beta = 90.3653(6) degrees, V = 3267.74(8) Å(3), Z = 8. {eta(3)-MeSi(CH(2)SMe)(3)}Mo(CO)(3) is monoclinic, P2(1)/c, a = 8.34630(6) Å, b = 15.2747(2) Å, c = 27.1865(4) Å, beta = 90.8987(9) degrees, V = 3465.44(10) Å(3), Z = 8. {eta(3)-MeSi(CH(2)SMe)(3)}W(CO)(3) is monoclinic, P2(1)/c, a = 8.1582(2) Å, b = 14.9903(2) Å, c = 26.7268(4) Å, beta = 90.6568(8) degrees, V = 3268.30(9) Å(3), Z = 8.

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PubMed1998

Approaches to Alkaline Earth Metal-Organic Chemical Vapor Deposition Precursors. Synthesis and Characterization of Barium Fluoro-beta-ketoiminate Complexes Having Appended Polyether "Lariats"

The synthesis and characterization of a family of beta-ketoimines derived from 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hfa) and the corresponding volatile barium beta-ketoiminate-polyether complexes having the general formula Ba[CF(3)COCHC(NR)CF(3)](2) where R = (CH(2)CH(2)O)(2)CH(3), (CH(2)CH(2)O)(2)CH(2)CH(3), and (CH(2)CH(2)O)(3)CH(2)CH(3) is reported. These complexes can be transported in the vapor phase at 160 degrees C/0.05 Torr without decomposition. The beta-ketoiminate ligands are synthesized by condensation of the appropriate amine-terminated poly(ethylene oxide)s with the trimethylsilyl enol ether derivative of hfa and converted to barium beta-ketoiminate-polyether complexes by reaction with BaH(2). The poly(ethylene oxide) amines are in turn synthesized by triphenylphosphine-mediated reduction of the corresponding poly(ethylene oxide) azides (synthesized via the tosylates) to afford the amines in good yields and analytical purity. The amines, beta-ketoimines, and barium complexes were characterized by elemental analysis, (1)H, (19)F, and (13)C NMR spectroscopy, mass spectroscopy, and thermogravimetric analysis. The eight- and ten-coordinate Ba(2+) complexes having the formula Ba[CF(3)COCHC(NR)CF(3)](2) where R = (CH(2)CH(2)O)(2)CH(2)CH(3) [C(22)H(28)N(2)F(12)O(6)Ba; space group = monoclinic, P2(1); a = 12.1175(2) Å, b = 14.9238(2) Å, c = 16.9767(3) Å, alpha = gamma = 90 degrees, beta = 90.0840(10) degrees, Z = 4] and R = (CH(2)CH(2)O)(3)CH(2)CH(3) [C(26)H(36)N(2)F(12)O(8)Ba; space group = triclinic, P&onemacr; (#2); a = 10.971(2) Å, b = 12.134(2) Å, c = 15.280(4) Å, alpha = 89.94(2) degrees, beta = 110.00(2) degrees, gamma = 116.75(2) degrees, Z = 2] were characterized by single-crystal X-ray diffraction. Both analyses reveal monomeric structures with the beta-ketoiminate ligands coordinated to the Ba(2+) center through all available oxygen and nitrogen atoms. These complexes are substantially more volatile than Ba(2,2,6,6,-tetramethyl-3,5-heptanedionate)(2) but less so than the most volatile Ba(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)(2).polyether complexes.

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PubMed1998

Molecular Structures of the Heavier Alkali Metal Salts of Supermesitylphosphane: A Systematic Investigation.

The molecular structures of the rubidium and cesium derivatives of supermesitylphosphane [i.e., (2,4,6-(t)Bu(3)C(6)H(2))PH(2) = (t)Bu(3)MesPH(2)] as well as several base adducts of these are reported. Sodium hydride, potassium hydride, rubidium metal, and cesium metal react with (t)Bu(3)MesPH(2) in tetrahydrofuran solution at room temperature to produce MPRH salts 1-4 [M = Na (1), K (2), Rb (3), Cs (4); R = (t)Bu(3)Mes] in good yields. X-ray-quality crystals of 2 and 3 were obtained by slow evaporation of solutions of the corresponding MP(H)(t)Bu(3)Mes species dissolved in toluene/thf. Complex 4 was crystallized from hot toluene. On the other hand, slow evaporation of a toluene/tetrahydrofuran solution of CsP(H)(t)Bu(3)Mes (4) produces crystals of the composition {[CsP(H)(t)Bu(3)Mes](2)(&mgr;-THF)(0.9).toluene}(x)() (5). Crystallization of 4 in the presence of pyridine yields crystals of {[CsP(H)(t)Bu(3)Mes](2)(&mgr;-pyridine)}(x)() (6). Also, crystallization of complexes 3 and 4 from toluene/N-methylimidazole (N-MeIm) gives the isomorphous complexes {[RbP(H)(t)Bu(3)Mes](2)(&mgr;-N-MeIm)}(x)() (7) and {[CsP(H)(t)Bu(3)Mes](2)(&mgr;-N-MeIm)}(x)() (8), respectively. However, crystallization of 4 from toluene in the presence of bidentate or polydentate bases such as dimethoxyethane or pentamethyldiethylenetriamine does not result in incorporation of these bases into the lattice. Instead, the toluene solvate {[CsP(H)(t)Bu(3)Mes](2)(eta(3)-toluene)(0.5)}(x)() (9) is obtained. On the other hand, crystallization of 4 from toluene/ethylenediamine gives the base adduct {[CsP(H)(t)Bu(3)Mes](2)(&mgr;-ethylenediamine)}(x)() (10). Complex 3 crystallizes in the triclinic space group P&onemacr;. Crystal data for 3 at 218 K: a = 6.71320(10) Å, b = 10.5022(2) Å, c = 14.9733(3) Å, alpha = 91.3524(13) degrees, beta = 102.5584(13) degrees, gamma = 107.7966(14) degrees; Z = 1; R(1) = 6.55%. Complex 4 crystallizes in the triclinic space group P&onemacr;. Crystal data for 4 at 223 K: a = 7.0730(14) Å; b = 10.395(2) Å; c = 14.933(2) Å; alpha = 81.97(1) degrees; beta = 76.35(2) degrees; gamma = 71.824(14) degrees; Z = 1; R(1) = 4.56%. Complex 5 crystallizes in the monoclinic space group P2(1)/c. Crystal data for 5 at 243 K: a = 15.039(2) Å; b = 16.152(3) Å; c = 20.967(5) Å; beta = 91.53(2) degrees; Z = 4; R(1) = 4.83%. Complex 6 crystallizes in the orthorhombic space group Pbcn. Crystal data for 6 at 298 K: a = 14.686(2) Å; b = 21.295(5) Å; c = 28.767(5) Å; Z = 8; R(1) = 5.61%. Complex 7 crystallizes in the orthorhombic space group Pbcn. Crystal data for 7 at 218 K: a = 14.5533(2) Å; b = 21.4258(5) Å; c = 28.5990(5) Å; Z = 8; R(1) = 4.61%. Complex 8 crystallizes in the orthorhombic space group Pbcn. Crystal data for 8 at 219 K: a = 14.6162(2) Å; b = 21.3992(3) Å; c = 28.7037(2) Å; Z = 8; R(1) = 3.57%. Complex 9 crystallizes in the triclinic space group P&onemacr;. Crystal data for 9 at 293 K: a = 11.147(4) Å; b = 14.615(4) Å; c = 14.806(5) Å; alpha = 70.57(3) degrees; beta = 71.85(3) degrees; gamma = 72.93(2) degrees; Z = 2; R(1) = 5.13%. Complex 10 crystallizes in the triclinic space group P&onemacr;. Crystal data for 10 at 173 K: a = 10.5690(4) Å; b = 15.0376(5) Å; c = 15.3643(5) Å; alpha = 111.8630(10) degrees; beta = 100.4120(10) degrees; gamma = 97.4820(2) degrees; Z = 2; R(1) = 4.87%. A common feature of the molecular structures of complexes 2-10 is an infinitely extended polymeric ladder framework in the solid state. Both solution and solid-state NMR data are presented.

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PubMed1998

Adducts of Titanium Tetrachloride with Alkylselenium Compounds: Molecular Precursors to Titanium Diselenide Films.

Treatment of titanium tetrachloride (2 equiv) with dimethyl diselenide or diethyl diselenide (1 equiv) in hexane at 0 degrees C, followed by crystallization at -20 degrees C, afforded (TiCl(4))(2)(Se(2)(CH(3))(2)) (78%) and (TiCl(4))(2)(Se(2)(CH(2)CH(3))(2)) (63%), respectively, as red and orange crystalline solids. (TiCl(4))(2)(Se(2)(CH(2)CH(3))(2)) is stable in solution and in the solid state at 23 degrees C, but (TiCl(4))(2)(Se(2)(CH(3))(2)) decomposes to TiCl(4)(Se(CH(3))(2))(2), gray selenium, and other products upon standing in hexane solution, in the solid state, or upon sublimation at 250 degrees C. Treatment of titanium tetrachloride with 2 equiv of dimethyl selenide or diethyl selenide in hexane at ambient temperature afforded a spectroscopically pure brick red solid of TiCl(4)(Se(CH(3))(2))(2) (96%) or TiCl(4)(Se(CH(2)CH(3))(2))(2) (96%), respectively. X-ray crystal structures of (TiCl(4))(2)(Se(2)(CH(2)CH(3))(2)), TiCl(4)(Se(CH(3))(2))(2), and TiCl(4)(Se(CH(2)CH(3))(2))(2) were determined to establish solid state nuclearities. (TiCl(4))(2)(Se(2)(CH(2)CH(3))(2)) crystallizes in the hexagonal space group P3(1)21 with a = 12.106(1) Å, c = 10.786(1) Å, V = 1368.8(4) Å(3), and Z = 3. TiCl(4)(Se(CH(3))(2))(2) crystallizes in the monoclinic space group P2(1)/n with a = 8.175(1) Å, b = 13.051(1) Å, c = 16.871(3) Å, beta = 102.675(8) degrees, V = 1756.3(2) Å(3), and Z = 4. TiCl(4)(Se(CH(2)CH(3))(2))(2) crystallizes in the monoclinic space group P2(1)/n with a = 6.404(4) Å, b = 16.376(7) Å, c = 13.058(8) Å, beta = 101.45(4) degrees, V = 1342(1) Å(3), and Z = 4. TiCl(4)(Se(CH(3))(2))(2) and TiCl(4)(Se(CH(2)CH(3))(2))(2) were evaluated as precursors to titanium diselenide films. TiCl(4)(Se(CH(3))(2))(2) was not a good precursor, but TiCl(4)(Se(CH(2)CH(3))(2))(2) afforded rose-bronze colored titanium diselenide films at substrate temperatures of 500-600 degrees C. The films were characterized by X-ray powder diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. Surprisingly, titanium diselenide films prepared from TiCl(4)(Se(CH(2)CH(3))(2))(2) are moisture sensitive and are apparently hydrolyzed by ambient moisture to titanium dioxide and hydrogen selenide. The relevance of the coordination chemistry to the development of precursors to titanium diselenide films is discussed.

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PubMed1997

Metallo 2,3-Disulfidothienoquinoxaline, 2,3-Disulfidothienopyridine, and 2-Sulfido-3-oxidothienoquinoxaline Complexes: Synthesis and Characterization.

The 2,3-disulfidothienoquinoxaline complexes of Cp(2)Mo and dppePd and the 2,3-disulfidothienopyridine complexes of Cp(2)Mo were obtained as products from the S(8) oxidation of the corresponding metallo-1,2-enedithiolate complexes. The analogous 2-sulfido-3-oxidothienoquinoxaline complexes of Cp(2)Ti, Cp(2)Mo, dppPd, and dppePt were prepared from 1-(quinoxalin-2-yl)-2-bromoethanone and the corresponding polysulfido complex. Both Cp(2)Mo{S(2)C(10)H(4)N(2)S} and Cp(2)Mo{SOC(10)H(4)N(2)S} have been characterized crystallographically. These complexes contain an extended planar ring where the metal is bound to substituents at the 2- and 3-positions of the thiophene ring. The oxidation products of the Cp(2)Mo derivatives all have EPR g values near 1.98 and (97/95)Mo hyperfine of </= 8.5 G. All of the complexes have a visible band assigned to an intraligand transition (IL). The excitation of a room-temperature DMSO solution of dppePt{SOC(10)H(4)N(2)S} leads to an emission at 690 nm with a phi = 0.005. Lifetime measurements were best fit as the sum of two exponential decays with lifetimes of 6 and 0.3 ns.

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PubMed1996

Metal Complexes of Mesitylphosphine: Synthesis, Structure, and Spectroscopy.

A series of primary phosphine homoleptic complexes [ML(4)](n)()(+)X(n)() (1, M = Ni, n = 0; 2, M = Pd, n = 2, X = BF(4); 3, M = Cu, n = 1, X = PF(6); 4, M = Ag, n = 1, X = BF(4); L = PH(2)Mes, Mes = 2,4,6-Me(3)C(6)H(2)] was prepared from mesitylphosphine and Ni(COD)(2), [Pd(NCMe)(4)][BF(4)](2), [Cu(NCMe)(4)]PF(6), and AgBF(4), respectively. Reactions of 1-4 with MeC(CH(2)PPh(2))(3) (triphos) or [P(CH(2)CH(2)PPh(2))(3)] (tetraphos) afforded the derivatives [M(L')L](n)()(+)X(n)() (L' = triphos; 6, M = Ni, n = 0; 7, M = Cu, n = 1, X = PF(6); 8, M = Ag, n = 1, X = BF(4); L' = tetraphos; 9, M = Pd, n = 2, X = BF(4)). Addition of NOBF(4) to 1 yielded the nitrosyl compound [NiL(3)(NO)]BF(4), 5. The solution structure and dynamics of 1-9 were studied by (31)P NMR spectroscopy (including the first reported analyses of a 12-spin system for 1-2). Complexes 1, 3, 6, and 7.solvent were characterized crystallographically. The structural and spectroscopic studies suggest that the coordination properties of L are dominated by its relatively small cone angle and that the basicity of L is comparable to that of more commonly used tertiary phosphines.

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PubMed1996

Syntheses of Cationic, Six-Coordinate Cadmium(II) Complexes Containing Tris(pyrazolyl)methane Ligands. Influence of Charge on Cadmium-113 NMR Chemical Shifts.

Treating a thf (thf = tetrahydrofuran) suspension of Cd(acac)(2) (acac = acetylacetonate) with 2 equiv of HBF(4).Et(2)O results in the immediate formation of [Cd(2)(thf)(5)](BF(4))(4) (1). Crystallization of this complex from thf/CH(2)Cl(2) yields [Cd(thf)(4)](BF(4))(2) (2), a complex characterized in the solid state by X-ray crystallography. Crystal data: monoclinic, P2(1)/n, a = 7.784(2) Å, b = 10.408(2) Å, c = 14.632(7) Å, beta = 94.64(3) degrees, V = 1181.5(6) Å(3), Z = 2, R = 0.0484. The geometry about the cadmium is octahedral with a square planar arrangement of the thf ligands and a fluorine from each (BF(4))(-) occupying the remaining two octahedral sites. Reactions of [Cd(2)(thf)(5)](BF(4))(4) with either HC(3,5-Me(2)pz)(3) or HC(3-Phpz)(3) yield the dicationic, homoleptic compounds {[HC(3,5-Me(2)pz)(3)](2)Cd}(BF(4))(2) (3) and {[HC(3-Phpz)(3)](2)Cd}(BF(4))(2) (4) (pz = 1-pyrazolyl). The solid state structure of 3 has been determined by X-ray crystallography. Crystal data: rhombohedral, R&thremacr;, a = 12.236(8) Å, c = 22.69(3) Å, V = 2924(4) Å(3), Z = 3, R = 0.0548. The cadmium is bonded to the six nitrogen donor atoms in a trigonally distorted octahedral arrangement. Four monocationic, mixed ligand tris(pyrazolyl)methane-tris(pyrazolyl)borate complexes {[HC(3,5-Me(2)pz)(3)][HB(3,5-Me(2)pz)(3)]Cd}(BF(4)) (5), {[HC(3,5-Me(2)pz)(3)][HB(3-Phpz)(3)]Cd}(BF(4)) (6), {[HC(3-Phpz)(3)][HB(3,5-Me(2)pz)(3)]Cd}(BF(4)) (7), and {[HC(3-Phpz)(3)][HB(3-Phpz)(3)]Cd}(BF(4)) (8) are prepared by appropriate conproportionation reactions of 3or 4 with equimolar amounts of the appropriate homoleptic neutral tris(pyrazolyl)borate complexes [HB(3,5-Me(2)pz)(3)](2)Cd or [HB(3-Phpz)(3)](2)Cd. Solution (113)Cd NMR studies on complexes 3-8 demonstrate that the chemical shifts of the new cationic, tris(pyrazolyl)methane complexes are very similar to the neutral tris(pyrazolyl)borate complexes that contain similar substitution of the pyrazolyl rings.

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PubMed1996

Regioselective Substitution Reactions of Sulfur(VI)-Nitrogen-Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl(2))(2)] (X = Cl or F) with Oxygen-Based Nucleophiles.

The reactions of the cyclic thionylphosphazenes [NSOX(NPCl(2))(2)] (1, X = Cl; 2, X = F) with three oxygen-based nucleophiles of increasing basicity, sodium phenoxide (NaOPh), sodium trifluoroethoxide (NaOCH(2)CF(3)), and sodium butoxide (NaOBu) have been studied. The reaction of 1 and 2 with 4 equiv of NaOPh at 25 degrees C yielded the regioselectively tetrasubstituted species [NSOX{NP(OPh)(2)}(2)] (5d, X = Cl; 6d, X = F). Further reaction of 5d with an additional 2 equiv of NaOPh over several days or at elevated temperatures gave the fully substituted compound [NSO(OPh){NP(OPh)(2)}(2)] (5e), whereas 6d did not react further. The reaction of 1 and 2 with 5 equiv of NaOCH(2)CF(3) yielded in both cases [NSO(OCH(2)CF(3)){NP(OCH(2)CF(3))(2)}(2)] (7e), and similarly reaction with 5 equiv of NaOBu yielded [NSO(OBu){NP(OBu)(2)}(2)] (9e). In all cases, the reactions were monitored by (31)P NMR and (where applicable) (19)F NMR and were found to involve complete substitution at phosphorus via a predominantly vicinal pathway, followed by substitution at sulfur. Substitutional control of the reactions of NaOPh, NaOBu, with 1 and 2 was found to conform to the following general order of reactivity, PCl(2) > PCl(OR) > SOX (X = Cl, F). Although the reaction with NaOCH(2)CF(3) followed the same order of reactivity, a significant enhancement of reaction rate was detected with each equivalent of trifluoroethoxide added. Reaction of 7e with excess NaOCH(2)CF(3) led to elimination of (CF(3)CH(2))(2)O and the formation of the salts Na[NSO(OCH(2)CF(3))NP(OCH(2)CF(3))(2)NP(OCH(2)CF(3))O] (11) and Na[NS(O)O{NP(OCH(2)CF(3))(2)}(2)] (12). Crystals of 6d are triclinic, space group P&onemacr;, with a = 9.789(3) Å, b = 11.393(4) Å, c = 12.079(5) Å, alpha = 107.40(3) degrees, beta = 91.23(3) degrees, gamma = 93.18(3), V = 1283.6(8) Å(3), and Z = 2. Crystals of 5e are monoclinic, space group C2/c, with a = 32.457(3) Å, b = 10.747(1) Å, c = 18.294(2) Å, beta = 110.37(1) degrees, V = 5982.4(9) Å(3), and Z = 8.

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PubMed1996

Synthesis and Ligand Substitution Reactions of a Mesitylphosphido-Bridged Platinum(II) Dimer.

The stable primary phosphine complexes trans-M(PH(2)Mes)(2)Cl(2) (1, M = Pd; 2, M = Pt; Mes = 2,4,6-(t-Bu)(3)C(6)H(2)) were prepared from Pd(PhCN)(2)Cl(2) and K(2)PtCl(4), respectively. Reaction of Pt(COD)Cl(2) (COD = 1,5-cyclooctadiene) with less bulky arylphosphines gives the unstable cis-Pt(PH(2)Ar)(2)Cl(2) (3, Ar = Is = 2,4,6-(i-Pr)(3)C(6)H(2); 4, Ar = Mes = 2,4,6-Me(3)C(6)H(2)). Spontaneous dehydrochlorination of 4 or direct reaction of K(2)PtCl(4) with 2 equiv of PH(2)Mes gives the insoluble primary phosphido-bridged dimer [Pt(PH(2)Mes)(&mgr;-PHMes)Cl](2) (5), which was characterized spectroscopically, including solid-state (31)P NMR studies. The reversible reaction of 5 with PH(2)Mes gives [Pt(PH(2)Mes)(2)(&mgr;-PHMes)](2)[Cl](2) (6), while PEt(3) yields [Pt(PEt(3))(2)(&mgr;-PHMes)](2)[Cl](2) (7), which on recrystallization forms [Pt(PEt(3))(&mgr;-PHMes)Cl](2) (8). Complex 5 and PPh(3) afford [Pt(PPh(3))(&mgr;-PHMes)Cl](2) (9). Addition of 1,2-bis(diphenylphosphino)ethane (dppe) to 5 gives the dicationic [Pt(dppe)(&mgr;-PHMes)](2)[Cl](2) (10-Cl), which was also obtained as the tetrafluoroborate salt 10-BF(4)() by deprotonation of [Pt(dppe)(PH(2)Mes)Cl][BF(4)] (11) with Et(3)N or by reaction of [Pt(dppe)(&mgr;-OH)](2)[BF(4)](2) with 2 equiv of PH(2)Mes. Complexes 8, 9, and 10-Cl.2CH(2)Cl(2).2H(2)O were characterized crystallographically.

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