Reactivity of molecules containing element-element bonds. 2. Transition elements [Erratum to document cited in CA114(15):143614m] (original) (raw)
Related papers
Inorganic Chemistry, 1975
(as3)?] BPh4, has also shown the presence of three hydridic hydrogen atoms and a similar molecular geometry to the iron compound is suggested, Furthermore the strict geometrical similarity of the cobalt and arsenic atoms in this structure (Figure 3) to the iron and phosphorus atoms in the preceding structure suggests that in the cobalt compound there are also three bridging hydridic hydrogen atoms to complete a confacial-bioctahedral geometry. Also for this structure at this point of refinement (R = 8.2%) a-IF Fourier synthesis was calculated. This map revealed three maxima with intensity of about 0.5 e/A3 in the expected positions. A AF Fourier, limited to the reflections having (sin 6)/X 5 0.30 A-1, confirmed the presence of these three peaks which then were considered hydrogen atoms. A least-squares refinement of these atoms resulted in a certain shift in their positions and furthermore yielded temperature factors rather high. However there was not any divergence during this refinement. Also in this case the positions obtained from the AF Fourier synthesis showed a more regular geometry and appeared more realistic. For this reason in the final structure factor calculation the three hydrogen atoms were introduced into the positions obtained from the ,IF' Fourier and assigned an overall isotropic temperature factor, B, equal to 5 A2. The final R factor is 8.2%. Tables VI and VI1 give the final positional and thermal parameters of the atoms of the complex. Table V I also includes the refined parameters of the bridging hydrogen atoms. Acknowledgment. Thanks are expressed to Professor L. M. Venanzi for the 31P nmr measurements, Mr. F. Cecconi and M r. D. Masi for technical assistance, Mr. G. Vignozzi and M r. F. Nuzzi for microanalyses. Registry Yo. [FezH3(p3)z]PFs.l.jCH2C12, 54003-33-7: [FezH3(p3)z] BPh4. 41 5 17-54-8: [CozH3(p3)2] BPh4, 54003-35-9; [CozH3(as3)z]BPh4, 54036-76-9; [Co(p3)(CO)z]BPh4, 54003-37-1; Supplementary Material Available. Listings of structure factor amplitudes for [FezH3(p3):]PFo 1 SCHzC12 and [CozH3(as3)z]BPh4 will appear following these pages in the microfilm edition of this volume of the journal, Photocopies of the supplementary material from this paper only or microfiche (105 X 148 mm, 24X reduction, negatives) containing all of the supplementary material for the papers in this issue may be obtained from the Journals Department. American Chemical Society,
6.10a. Inorg. Chem. 31,1233.pdf
The ruthenium complex [Ru2(CloHsN2)(CO),(PiPr3),] (1) (CloHIoN2 = 1,8-diaminonaphthalene) reacts with 1 equiv of HgX, (X = C1, Br, I, 02CCH,, 02CPh, 02CCH2C1, 02CCF3, SCN, ONC) to give the adducts [(1)HgX2], in which the Hg atoms are bonded to both Ru atoms of complex 1. Correlations between the 2J(3'P-199Hg) coupling constants of their 31P NMR spectra and the corresponding halogen electronegativities or acid pK,s have been observed. With the exception of [(1)Hg(O2CCF,),], which does not react with any other mercury(I1) salt, the compounds [(l)HgX,] react with HgX', (X' = C1, Br, I, 02CCH3, 02CPh, 02CCH2C1) to give the insertion products [(l)Hg(p-X'),HgX,] only when X' is more electron-withdrawing than X; otherwise, the addition products [(l)Hg(pX),HgX',] are formed. All reactions of [(l)HgX,] with Hg(02CCF3), give the same substitution product [(l)Hg(02CCF3)2]. The molecular structures of [(l)Hg(O,CCF,),] and [(l)Hg(p-Cl),HgCI,] have been confirmed by X-ray crystallography. [(l)Hg(O,CCF,),]: monoclinic, space group C2/c, a = 23.730 (9) A, b = 12.578 (4) A, c = 14.51 1 (7) A, fl = 94.76 (5)O, Z = 4. [(1)Hg(p-C1),HgC1,]~CH2Cl2: monoclinic, space group P 2 , / n , a = 15.840 (7) A, b = 12.694 (4) A, c = 23.366 (2) A, fl = 105.74 (2)O, Z = 4. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Garda-Granda, S.; Van Der Maelen, J. F. Inorg. Chim. Acta 1991, 185, 187. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Pellinghelli, M. A.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1991, 371. Andreu, P. L.; Cabeza, J. A.; Riera, V.; Robert, F.; Jeannin, Y. J. Organomet. Chem. 1989, 372, C15. Oro, L. A.; Fernindez, M. J.; Modrego, J.; Foces-Foces, C.; Cano, F. H. Angew. Chem., Inr. Ed. Engl. 1984, 23, 913. Fernindez, M. J.; Modrego, J.; Oro, L. A.; Apreda, M. C.; Cano, F. H.; Foces-Foces, C. J. Chem. SOC., Dalton Trans. 1989, 1249. See, for example: Panizo, M.; Cano, M. J. Organomet. Chem. 1984, 266,247. Pardo, M. P.; Cano, M. J. Organomet. Chem. 1983,247,293. Faraone, F.; Lo Schiavo, S.; Bruno, G.; Bombieri, G. J. Chem. Soc., Chem. Commun. 1984, 6. (a) Ermer, S.; King, K.; Rosenberg, E.; Manotti-Lanfredi, A. M.; Tiripicchio, A.; Tiripicchio-Camellini, M. Inorg. Chem. 1983, 22, 1339. (b) Rosenberg, E.; Ryckman, D.; Hsu, I.-N.; Gellert, R. W. Inorg. Chem. 1986, 25, 194. (c) Rosenberg, E.; Hardcastle, K. I.; Day, M. W.; Gobetto, R.; Hajela, S.; Muftikian, R. Organometallics 1991, 10, 203. (d) Fadel, S.; Deutcher, J.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1977, 16, 704. (e) Fajardo, M.; Holden, H. D.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R. J. Chem. SOC., Chem. Commun., 1984, 24. (f) G6mez-Sa1, M. P.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R.; Syed-Mustaffa, S. N. A. B.
Inorganic Chemistry, 1995
The thorium metallacycle [(Me3Si)2N]2h[N(SiMe3)(SiMe2kH2)] (1) reacts with 4 equiv of 2,4-dimethylpentan-3-01 (diisopropylmethanol) in toluene at room temperature to produce dimeric Thz(0R)g (2) (R = CH-i-Pr2). IH NMR spectra of 2 in noncoordinating solvents indicate a monomer-dimer equilibrium in solution at ambient temperatures between 2 and its monomer Th(OR)4 (3). Thermodynamic parameters for the equilibrium process are A W = 17 kcal mol-I, AG" = 5 kcal mol-', AS" = 40 cal mol-' K-I. Addition of Lewis bases such as DME (DME = 1,2-dimethoxyethane), pyridine or quinuclidine to solutions of 2 results in the formation of the five-and six-coordinate mononuclear adducts Th(OR)d(DME) (4), Th(OR)d(py)~ (S), and Th(OR)4(quin) (6), respectively. Reaction of 5 with 1 equiv of Me3SiI produces the monoiodide derivative ThI(OR)3(py)z (7). Compounds 2-7 have been characterized by 'H NMR and IR spectroscopy, by elemental analysis, and, in the case of 2, 6, and 7, by single crystal X-ray diffraction studies. Th2(OCH-i-Prz)g (2) exhibits a dimeric structure in which the Th208 core can be viewed as two Tho5 trigonal bipyramids joined along a common axial-equatorial edge. Terminal Th-0 distances average 2.154( 11) 8, while bridging Th-0 distances are significantly longer at 2.436(11) 8, (average). Th(OCH-i-R2)4(quin) (6) displays a trigonal bipyramidal geometry with the quinuclidine ligand occupying an axial site. Th-0 distances average 2.165(17) 8, while the Th-N distance is 2.712(11) A. ThI-(OCH-i-Pr2)3(py)2 (7) exhibits a facial pseudooctahedral geometry in the solid state, with Th-0 and Th-N distances averaging 2.136(8) and 2.746(9) A, respectively, and a Th-I distance of 3.226(1) A. C stal data for 2 at -170 "C: monoclinic space group P2lln, a = 12.115(2) A, b = 20.820(3) A, c = 13.002(2) x , /3 = 100.62(1)", V = 3223.4 A3, dcalcd = 1.428 g ~m -~, Z = 2. Crystal data for 6 at -70 "C: monoclinic space group Cc, a = 18.778-(3) A, b = 11.391(2) A, c = 20.538(3) A, /3 = 113.51(2)", v = 4028.4 A3, dcalcd = 1.356 g ~m -~, = 4. Crystal data for 7 at -70 "C: triclinic space group Pi, a = 9.691(2) A, b = 11.739(2) A, c = 17.006(3) A, a = 77.63-(3)", p = 75.34(3)", y = 72.41(2)", V = 1764.1 A3, dcalcd = 1.624 g cm-3, Z = 2.
Organometallics, 1987
The reaction of Pb(C0)3(P-t-BuzPh)3 (1) with 3 equiv of HCl at-50 O C results in immediate formation of PtHCl(CO)(P-t-Bu,Ph) (2) in which the hydride ligand is assigned to the position trans to the CO ligand. Complex 2 isomerizes rapidly at higher temperatures to give a second complex, PtHCl(CO)(P-t-BuzPh) (3), with the hydride ligand trans to the chloride ligand. Complex 3 slowly converts to a dinuclear Pt(1) complex shown by X-ray crystallography to be PtzC1z(CO)2(P-t-Bu2Ph)z (4). Complex 4 crystallizes in the monoclinic space group P2Jc with 2 = 4 in a unit cell of dimensions a = 15.418 (1) A, b = 14.751 (1) A, c = 16.051 (2) A, and p = 108.61 (1)". The structure was refined by using 4065 independent reflections with 203 variables to R1 = 0.046 and Rz = 0.053. 4 contains an unsupported Pt-Pt bond (2.628 (1) A), and the phosphine ligands are located trans to this bond. The Pt atom coordination spheres are essentially square-planar with a dihedral angle of 109.9" between the two planes. The rotational energy of the Pt-Pt bond and the relative stability of 4 and a hypothetical C1-bridged isomer are examined by using EHMO calculations. 4 also can be prepared by reacting 1.5 equiv of Clz with 1 while reaction of 1 or 4 with excess C12 gives Pt(Cl),(CO)(P-t-BuPh) (7). Addition of excess NaBH4 to a solution of 3 regenerates 1, and reaction of 3 with AgPF6 gives [ (Pt3(~-C0)3(P-t-Bu2Ph)3)zAg] [PF6] (6). Complex 6 has been spectroscopically characterized as a Ag cation sandwiched between two units of 1. 6 is also the product of the reaction of 1 and AgPF,. a Estimated standard deviations in the least significant figure(s) are given in parentheses. Anisotropically refined atoms are given in the form of the isotropic equivalent thermal parameter defined as (4/3)[a2~(1,i) + ~~(2 , 2) + c*~(3,3) + ab(cos y)~(1,2) + ac(cos B)B(1,3) + bc(cos a)B(2,3)]. cipitate was obtained by filtration; yields are quantitative; 'H
Zeitschrift Fur Kristallographie-new Crystal Structures, 2007
C 60H 56Cl 2 O 12PRu 2 ,orthorhombic, P 2 1 2 1 2 1 (no. 19), a =8.6267(7) Å, b =23.487(2) Å, c =28.700(2) Å, V =5815.1 Å 3 , Z =4, R gt (F) =0.064, wR ref (F 2) =0.184, T =296 K. Source of material Silver tetrafluoroborate (0.03 g, 0.17 mmol) wasadded to asolution of Ru 2 Cl(m-O 2 CCH 2 CH 2 OPh) 4 [1] (0.15 g, 0.17 mmol) in THF(30 mL). The reaction mixture wasstirred for 24 h, giving a solid precipitate of AgCland abrown solution. The precipitate wasfiltered through Celite and the solution waspumped to dryness. The solid wasd issolved in methanol (10 mL)and treated with amethanolsolution (5 mL)ofPPh 4 Cl(0.25 g, 0.68 mmol), giving abrown solid, which wasfiltered and dried under vacuum. Crystals suitablefor X-raystudies were grown by evaporation in air from asolutioninmethanol (20 mL).
53 The investigation of crystal structure, spectroscopic an
The two new azo dyes p-(p-acetylphenylazo)-o-allylphenol (compound I) and p-(p-bromphenylazo)-o-allylphenol (compound II) have been synthesized and studied by FT-IR, UVeVIS, 1 H NMR, 13 C NMR techniques, elemental analysis, X-ray structure analysis and TG, DTG, and DTA analyses. Compound I crystallizes in the monoclinic space group P21/c with a = 19.6130 Å , b = 7.3586(6) Å , c = 21.4752(15) Å , a = 90.00 , b = 101.413(6) , g = 90.00 , Z = 8, V = 3038.1(4) Å 3 and the molecules are linked by two intermolecular O/O hydrogen bonds. There are two independent molecules in the asymmetric unit of compound I. Compound II crystallizes in the monoclinic space group Cc with a = 4.7194(7) Å , b = 24.597(2) Å , c = 12.2241(16) Å , a = 90.00 , b = 96.509(11) , g = 90.00 , Z = 4, V = 1409.9(3) Å 3 and the molecules are linked by O/N and CeH/O intermolecular hydrogen bonds. They are characterized by UVeVIS, FT-IR, 1 H NMR, 13 C NMR techniques, elemental analysis, TG, DTG, and DTA analyses.
Inorganic Chemistry, 1984
The compound NazRu(CN),N0.2H20 has been synthesized from ruthenium trichloride and sodium cyanide by oxidation with nitric acid. The orange prismatic crystals belong to the orthorhombic space group Pnmm with a = 6.303 (2) A, b = 12.084 (4) A, c = 15.833 ( 5 ) A, and Z = 4. The structure was refined with use of the initial atomic coordinates from the isostructural sodium nitroprusside, NazFe(CN)SNO-2Hz0, to R = 0.030, R , = 0.028, for 1588 independent reflections; hydrogen atoms were then located in a difference Fourier synthesis and refined with use of constraints in bond lengths R = 0.024, R , = 0.023). Important bond lengths and angles are as follows:
Organometallics, 1992
The zirconium and sulfur atoms were located from a Patterson map: all remaining non-hydrogen atoms were obtained from Fourier maps. The data were refined as described for the structures discussed above. All non-hydrogen atoms were handled as described earlier. Final refinement of this solution yielded an R value of 2.33% (R, = 2.98%). Generation of the other enantiomorph and subsequent refinement converged to an R value of 2.26%, indicating that the second choice of polarity was correct. The final residuals for 324 variables refined against 1773 data for which F > 3o(F) were R = 2.26%, R, = 2.89%, and GOF = 1.17. The R value for all 1983 data was 2.77%. The quantity minimized by the least-squares program, p factor, and corrections for anomalous dispersion were also handled as described above. The largest peaks in the final difference Fourier map had an electron density of k0.23 e/A3. There was no indication of secondary extinction in the high-intensity, low-angle data. Synthesis of Cp*,Zr(SC(p-C6HICH3)=C(p-C6H,CH,)) (13c). As in the preparation of 13b, a benzene solution of complex lla (100 mg, 0.21 mmol) and 130 mg (0.63 mmol) of dip -tolylacetylene was thermolyzed in a degassed Pyrex bomb at 85 "C for 12 h. Excess alkyne was removed by sublimation at 85 "C onto a cold finger (under vacuum). Extraction of the red-orange residue into a minimum of benzene, filtration, and layering with hexane yielded 83 mg (65%) of microcrystalline material: IR
Acta Crystallographica Section C Crystal Structure Communications
CIaH22CIN20+.C4HsO6.C3HsO.½H20 AND C14H16NO~'.C4HsO6 chromated Mo Ka radiation. 20max = 54 °, h 0~ 12, k 0~ 18, l-8~8 for (I) and h 0~ 17, k 0-, 10, l-9 ~9 for (2). 1606 independent reflections for (1) and 1613 for (2) having I> 30-(/) were recorded in the range 2.5 < 0 < 27 °. Crystal dimensions were 0.2 x 0.3 x 0-4 mm for (1) and 0.3 x 0.4 x 0.3 mm for (2). (0 Lorentz-polarization corrections were applied. The o 0.7178 (1) structures were solved by direct methods, Ol 0.7902 (3) C1 0.8211 (4) MULTAN80 (Main, Fiske, Hull, Lessinger, c2 0.7686 (4) C3 0.6554 (4) Germain, Declercq & Woolfson, 1980). The H atoms ciA 0"7951 (4) of the phenyl, pyridyl, and pyrrolidinyl moieties were c2A 0.7628 (4) C3A 0.7396 (4) placed at the stereochemically expected positions, c4A 0.7493 (4) Subsequent difference Fourier syntheses located the csA 0.7819 (4) C6A 0.8049 (5) remaining H atoms. Full-matrix least-squares NIS 0'9697 (4) refinement minimized Y.w(IFol-IF~I) 2 with w-1= c~s 0'9344(4) C3B 0"9957 (5) 0.2(Fo) + (0"02Fo) 2 + 1 (Killean & Lawrence, 1969). c4n 1"0980 (5) Scale factor, atomic coordinates, and anisotropic css 1-1345(5) C6B 1.0681 (5) thermal parameters were refined for non-H atoms in N1C 0.6069 (3) both structures, except that the water oxygen in (1) c2c 0"6139(6) C3C 0"5329 (5) was treated as isotropic and of site occupancy 0.5. C4C 0.4555 (5) C5C 0'4974 (4)