Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalyse von cis-(Et4N)[OsF2Cl4] und trans-(Ph4P)[OsF2Cl4]

Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of cis -(Et₄N)[OsF₂Cl₄] and trans -(Ph₄P)[OsF₂Cl₄] By oxidation of the pure fluorochloroosmates(IV) with KBrF₄ or PbO₂/trifluoracetic acid in dichloromethane the mixed pentavalent complex anions cis-[OsF₂Cl₄]^– and trans-[OsF₂Cl₄]^– are formed. X-ray structure determinations on single crystals have been performed of cis-(Et₄N) · [OsF₂Cl₄] ( 1 ) (monoclinic, space group P2₁/n, a = 7.519(2), b = 17.648(2), c = 11.942(4) Å, β = 105.98(2)°, Z = 4) and trans-(Ph₄P)[OsF₂Cl₄] ( 2 ) (tetragonal, space group P4/n, a = 12.677(2), c = 7.743(1) Å, Z = 2). Based on the molecular parameters of the X-ray determinations and assuming C_2v point symmetry for the anion of 1 and D_4h point symmetry for the anion of 2 the IR and Raman spectra have been assigned by normal coordinate analysis. Due to the stronger trans influence of chlorine as compared with fluorine for F ^· –Os–Cl′ axes significally different valence force constants are observed in comparison with symmetrically coordinated axes: f_d(OsF ^· ) = 3.35, f_d(OsF) = 3.73, f_d(OsCl′) = 2.05 and f_d(OsCl) with 1.98 and 2.00 mdyn/Å.     

Darstellung,Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von K2[OsCl5(CO)] · H2O

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of K₂[OsCl₅(CO)] · H₂O The X-ray structure determination of K₂[OsCl₅(CO)] · H₂O (monoclinic, space group P2₁/c a = 13.600(2), b = 7.122(1), c = 22.186(11) Å, β = 98.66(3)°, Z = 8) revealed two crystallographic independent bat very similar complex anions [OsCl₅(CO)]^2? with rough C_4v point symmetry. Due to the stronger trans influence of the carbonyl group the bond lengths in the Cl? Os? CO axis Os? Cl = 2.449(2), 2.430(2) Å are langer as compared with the octahedron basis Os? Cl = 2.340-2.370 Å. The water of crystallization is coordinated to potassium (K? OH₂ = 2.625-2.815 Å). Using the molecular parameters the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(CO) = 15.30, f_d(OsC) = 3.88, f_d(OsCl) = 1.81, f_d(OsCl) = 1.36, f_d(OH) = 7.65, 7.82, 7.79 mdyn/Å. The strengthening of the Os? C bond by stronger back donation of the Os^III(d⁵) complex in comparison with the isostructural Os^IV (d⁴) compound is discussed.     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalyse von fac‐(Et4N)[OsF3Cl3] und fac‐(Et4N)[IrF3Cl3]

Crystal Structures, Vibrational Spectra and Normal Coordinate Analysis of fac ‐(Et₄N)[OsF₃Cl₃] and fac ‐(Et₄N)[IrF₃Cl₃] By careful oxidation of the pure fluorochloroosmates(IV) or ‐iridates(IV) with BrF₃ or KBrF₄ in dichloromethane the mixed pentavalent complex anions fac‐[OsF₃Cl₃]^– and fac‐[IrF₃Cl₃]^– are formed. X‐ray structure determinations on single crystals have been performed of cis‐(Et₄N)[OsF₃Cl₃] ( 1 ) (orthorhombic, space group Pbca, a = 11.225(5), b = 12.020(5), c = 21.873(5) Å, Z = 8) and fac‐(Et₄N)[IrF₃Cl₃] ( 2 ) (orthorhombic, space group Pbca, a = 11.269(10) b = 12.049(1), c = 21.801(3) Å, Z = 8). Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra for the anion of 1 and 2 have been assigned by normal coordinate analysis. The Osmium compound exhibits slightly higher valence force constants as compared with the Iridium complex: f_d(OsF) = 3.25, f_d(IrF) = 3.25, f_d(OsCl) = 2.35 and f_d(IrCl) = 2.25 mdyn/Å.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Trichlorotrirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of four Linkage Isomeric Trichlorotrirhodanoosmates(IV) By treatment of fac-[OsCl₃I₃]^2? with (SCN)₂ in dichloromethane the linkage isomers fac-[OsCl₃(NCS)₃]^2? ( 1 ), mer-[OsCl₃(NCS)₂^c(SCN)]^2? ( 2 ), mer-[OsCl₃(NCS)(SCN)₂^t]^2? ( 3 ), and mer-[OsCl₃(NCS)(SCN)₂^c]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations have been performed on single crystals of fac-(Ph₄As)₂[OsCl₃(NCS)₃] (triclinic, space group P1 , a = 12.142(5), b = 13.233(5), c = 19.300(5) Å, α = 98.642(5)º, β = 100.509(5)º, γ = 112.514(5)º, Z = 2), mer-(Ph₄As)₂[OsCl₃(NCS)₂^c (SCN)] · acetone (triclinic, space group P1 , a = 11.707(5), b = 13.238(5), c = 19.048(5) Å, α = 75.960(5)º, β = 88.981(5)º, γ = 69.999(5)º, Z = 2), mer-(Ph₄As)₂[OsCl₃(NCS)(SCN)₂ ^t] (triclinic, space group P1, a = 10.6861(12), b = 11.6587(5), c = 12.5232(5) Å, α = 112.069(8)º, β = 95.052(8)º, γ = 92.559(7)º, Z = 1) and mer-(Ph₄As)₂[OsCl₃(NCS)(SCN)₂ ^c] · 2acetone (triclinic, space group P1 , a = 11.444(5), b = 14.661(5), c = 15.830(5) Å, α = 75.790(5)º, β = 80.273(5)º, γ = 75.205(5)º, Z = 2). The complex anions are completely ordered. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 169.1º, 171.5º, 175.7º ( 1 ), 175.6º, 178.6º ( 2 ), 172º ( 3 ), and 173.1º ( 4 ) and Os? S? C angles of 106.2º ( 2 ), 106.1º, 106.6º ( 3 ), 105.1º, and 108.2º ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers have been assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.71 ( 1 ), 1.46 and 1.62 ( 2 ), 1.69 ( 3 ), and 1.61 ( 4 ), f_d(OsS) = 1.27 ( 2 ), 1.36 ( 3 ), 1.32, and 1.49 mdyn/Å ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Tetrachlorodirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of Four Linkage Isomeric Tetrachlorodirhodanoosmates(IV) By treatment of cis- or trans-[OsCl₄I₂]^2? with (SCN)₂ in dichloromethane the linkage isomers cis-[OsCl₄(NCS)₂]^2? ( 1 ), trans-[OsCl₄(NCS)(SCN)]^2? ( 2 ), cis-[OsCl₄(NCS)(SCN)]^2? ( 3 ) and trans-[OsCl₄(SCN)₂]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determinations on single crystals of cis-(Ph₄As)₂[OsCl₄(NCS)₂] (triclinic, space group P1 , a = 10.019(5), b = 11.702(5), c = 21.922(5) Å, α = 83.602(5)°, β = 85.718(5)°, γ = 73.300(5)°, Z = 2), trans-(Ph₄As)₂[OsCl₄ · (NCS)(SCN)] (monoclinic, space group P2₁/c, a = 18.025(5), b = 11.445(5), c = 23.437(5) Å, β = 94.208(5)°, Z = 4), cis-(Ph₄As)₂[OsCl₄(NCS)(SCN)] (triclinic, space group P1 , a = 10.579(5), b = 11.682(5), c = 22.557(5) Å, α = 81.073(5)°, β = 85.807(5)°, γ = 87.677(5)°, Z = 2) and trans-(Ph₄As)₂ · [OsCl₄(SCN)₂] (triclinic, space group P1 , a = 10.615(5), b = 11.691(5), c = 11.907(5) Å, α = 111.314(5)°, β = 96.718(5)°, γ = 91.446(5)°, Z = 1) reveal the complete ordering of the complex anions. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 171.2° and 174.3° ( 1 ), 162.3° ( 2 ), 172° ( 3 ) and Os? S? C angles of 108.3° ( 2 ), 105.7° ( 3 ) and 105.5° ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers are assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.59 ( 1 ), 1.67 ( 2 ), 1.60 ( 3 ) and f_d(OsS) = 1.27 ( 2 ), 1.31 ( 3 ) and 1.32 mdyn Å^?1 ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Kristallstruktur,Schwingungsspektren und Normalkoordinatenanalyse von K2[IrCl5(NH3)]

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of K₂[IrCl₅(NH₃)] The X-ray structure determination of K₂[IrCl₅(NH₃)] (orthorhombic, space group Pnma, a = 13.426(4), b = 10.015(2), c = 6.8717(7) Å, Z = 4) revealed the C_s point symmetry of the complex anion [IrCl₅(NH₃)]^2? (Ir? Cl = 2.337–2.365, Ir? N = 2.067(10); N? H = 0.73–0.79 Å). Using the molecular parameters the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(NH) = 5.88, f_d(IrN) = 2.66, f_d(IrCl) = 1.68 mdyn/Å.     

Darstellung,spektroskopische Charakterisierung und Kristallstrukturen von [(C5H5N)2CH2][PtCl5(SCN)] und cis-[(C5H5N)2CH2][PtCl4(SCN)2]

Preparation, Spectroscopic Characterization, and Crystal Structures of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] and cis -[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] By treatment of [PtCl₆]^2– with SCN^– in aqueous solution a mixture of chlorothiocyanatoplatinates(IV) is formed, from which [PtCl₅(SCN)]^2– and cis-[PtCl₄(SCN)₂]^2– have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations on single crystals of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] ( 1 ) (tetragonal, space group P 4₃, a = 7.687(1), c = 29.698(4), Z = 4) and cis-[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] ( 2 ) (monoclinic, space group P 2₁/n, a = 11.2467(9), b = 15.0445(10), c = 11.3179(13), β = 92.840(9)°, Z = 4) show, that the thiocyanate groups are coordinated via S atoms with average Pt–S distances of 2.339 Å and Pt–S–C angles of 104.7° up to 107.1°. Using the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra have been assigned by normal coordinate analyses. The valence force constants of the S–Pt–Cl˙ axes are f_d(PtS) = 1.81 ( 1 ) and 1.87 ( 2 ), f_d(PtCl ^× ) = 1.77 ( 1 ) and 1.81 ( 2 ), of the Cl–Pt–Cl axes are f_d(PtCl) = 1.93 ( 1 ) and 1.90 mdyn/Å ( 2 ). The ¹⁹⁵Pt NMR spectra from dichlormethane solutions exhibit each one sharp signal at 3975.6 ( 1 ) and 3231.6 ppm ( 2 ), respectively.     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalysen von (n-Bu4N)2[ReBr5(NCS)] und (n-Bu4N)2[ReBr5(NCSe)]

Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of ( n -Bu₄N)₂[ReBr₅(NCS)] and ( n -Bu₄N)₂[ReBr₅(NCSe)] The X-ray structure determinations on single crystals of (n-Bu₄N)₂[ReBr₅(NCS)] ( 1 ) (monoclinic, space group P2₁/n, a = 10.9860(9), b = 11.6860(7), c = 35.551(3) Å, β = 91.960(9)°, Z = 4) and (n-Bu₄N)₂[ReBr₅(NCSe)] ( 2 ) (monoclinic, space group P2₁/n, a = 11.0208(15), b = 11.7418(16), c = 35.621(12) Å, β = 92.003(18)°, Z = 4) reveal that the thiocyanate and the selenocyanate group are bonded with the Re–N–C angle of 168.5° ( 1 ) and 169.9° ( 2 ). Based on the molecular parameters of the X-ray determinations the IR and Raman spectra have been assigned by normal coordinate analysis. The valence force constants f_d(ReN) are 1.81 ( 1 ) and 1.75 mdyn/Å ( 2 ).     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen der Tetrahalogeno‐bis‐Pyridin‐Osmium(III)‐Komplexe cis‐(n‐Bu4N)[OsCl4Py2] und trans‐(n‐Bu4N)[OsX4Py2], X = Cl,Br

Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Tetrahalogeno‐bis‐Pyridine‐Osmium(III) Complexes cis ‐( n ‐Bu₄N)[OsCl₄Py₂] and trans ‐( n ‐Bu₄N)[OsX₄Py₂], X = Cl, Br By reaction of (n‐Bu₄N)₂[OsX₆], X = Cl, Br, with pyridine and (n‐Bu₄N)[BH₄] tetrahalogeno‐bis‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of cis‐(n‐Bu₄N)[OsCl₄Py₂] ( 1 ) (triclinic, space group P1, a = 9.4047(9), b = 10.8424(18), c = 17.007(2) Å, α = 71.833(2), β = 81.249(10), γ = 67.209(12)°, Z = 2), trans‐(n‐Bu₄N)[OsCl₄Py₂] ( 2 ) (orthorhombic, space group P2₁2₁2₁, a = 8.7709(12), b = 20.551(4), c = 17.174(4) Å, Z = 4) and trans‐(n‐Bu₄N)[OsBr₄Py₂] ( 3 ) (triclinic, space group P1, a = 9.132(3), b = 12.053(3), c = 15.398(2) Å, α = 95.551(18), β = 94.12(2), γ = 106.529(19)°, Z = 2). Based on the molecular parameters of the X‐ray structure determinations and assuming C₂ point symmetry for the anion of 1 and D_2h point symmetry for the anions of 2 and 3 the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants of 1 are in the Cl–Os–Cl axis f_d(OsCl) = 1.58, in the asymmetrically coordinated N′–Os–Cl ^· axes f_d(OsCl ^· ) = 1.45, f_d(OsN′) = 2.48, of 2 f_d(OsCl) = 1.62, f_d(OsN) = 2.42 and of 3 f_d(OsBr) = 1.39 and f_d(OsN) = 2.34 mdyn/Å.     

Neue Halogenochalkogen(IV)‐Säuren: [H3O(Benzo‐18‐Krone‐6)]2[Te2Br10] und [H5O2(Dibenzo‐24‐Krone‐8)]2[Te2Br10]

Novel Halogenochalcogeno(IV) Acids: [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] Systematic studies on halogenochalcogeno(IV) acids containing tellurium and bromine led to the new crystalline phases [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] ( 1 ) and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] ( 2 ). The [Te₂Br₁₀]^2‐ anions consists of two edge‐sharing distorted TeBr₆ octahedra, the oxonium cations are stabilized by crownether. ( 1 ) crystallizes in the monoclinic space group P2₁/n with a = 14.520(5) Å, b = 22.259(6) Å, c = 16.053(5) Å, β = 97.76(3)° and Z = 4, whereas ( 2 ) crystallizes in the triclinic space group with a = 11.005(4) Å, b = 12.103(5) Å, c = 14.951(6) Å, α = 71.61(3)°, β = 69.17(3)°, γ = 68.40(3)° and Z = 1.     

Kristallstrukturen und Normalkoordinatenanalyse der bindungsisomeren Pentachloroselenocyanatorhenate (IV)

Crystal Structure and Normal Coordinate Analysis of Linkage Isomeric Pentachloroselenocyanatorhenates (IV) The X-ray structure determinations on single crystals of (Ph₃PNPPh₃)₂[ReCl₅(NCSe)] ( 1 ) (monoclinic, space group P2₁/n, a = 10.806(2), b = 13.349(2), c = 46.071(4) Å, β = 94.947(9)°, Z = 4) and (Py₂CH₂)[ReCl₅(SeCN)] ( 2 ) (monoclinic, space group P2₁/n, a = 12.044(1), b = 9.838(1), c = 15.686(2) Å, β = 105.913(8)°, Z = 4) reveal, that the nearly linear selenocyanate group (178°) is coordinated via N with the Re–N–C angle of 172.7 ( 1 ) and via Se with the Re–Se–C angle of 107.4° ( 2 ). Based on the molecular parameters of the X-ray determinations the IR and Raman spectra, known from literature for both linkage isomers, have been assigned by normal coordinate analysis. The valence force constants are f_d(ReN) = 1.72 and f_d(ReSe) = 1.20 mdyn/Å.     

Darstellung von Nonahalogenodiplatinaten(IV), [Pt2X9]−, X  Cl,Br Spektroskopische Charakterisierung,Normalkoordinatenanalyse und Kristallstruktur von (PPN)[Pt2Br9]

Preparation of the Nonahalogenodiplatinates(IV), [Pt₂X₉]^?, X ? Cl, Br Spectroscopic Characterization, Normal Coordinate Analysis, and Crystal Structure of (PPN)[Pt₂Br₉] On heating the tetrabutylammonium salts (TBA)₂[PtX₆], with trifluoroacetic acid the nonahalogenodiplatinates(IV) (TBA)[Pt₂X₉], with X ? Cl, Br are formed. The X-ray structure determination on (PPN)[Pt₂Br₉] (orthorhombic, space group Pca2, Z = 4) shows for the anions pairs of face-sharing octahedra with nearly D_3h symmetry. The mean terminal and bridging Pt? Br bond lengths are determined to be 2.42 and 2.52 Å, respectively. The electrostatic interaction of the Pt atoms results in the Pt? Pt distance of 3.23 Å and an elongation as it has been forecasted by the MO scheme for d⁶ systems. Using the structural data a normal coordinate analysis based on a general valence force field for [Pt₂Br₉]^? has been performed, revealing a good agreement of the calculated frequencies with the bands observed in the IR and Raman spectra. The stronger bonding of the terminal as compared to the bridging ligands is shown by the valence force constants, f_a(Br₁) = 1,55 > f_d(Br_b) = 0,93 mdyn/ Å.     

Kristallstrukturen,Normalkoordinatenanalysen und 15N‐NMRund 77Se‐NMR‐Verschiebungen von trans‐[OsO2(NCO)4]2–, trans‐[OsO2(NCS)4]2– und trans‐[OsO2(SeCN)4]2–

Crystal Structures, Normal Coordinate Analyses, and ¹⁵N NMR and ⁷⁷Se NMR Chemical Shifts of trans ‐[OsO₂(NCO)₄]^2–, trans ‐[OsO₂(NCS)₄]^2–, and trans ‐[OsO₂(SeCN)₄]^2– The crystal structures of trans‐(Ph₃PNPPh₃)₂[OsO₂(NCO)₄] ( 1 ) (orthorhombic, space group Pbca, a = 19.278(3), b = 16.674(4), c = 19.982(2) Å, Z = 4), trans(n‐Bu₄N)₂[OsO₂(NCS)₄] ( 2 ) (triclinic, space group P1, a = 12.728(3), b = 12.953(3), c = 16.255(6) Å, α = 97.39(4), β = 105.62(2), γ = 95.25(3)°, Z = 2) and trans‐(n‐Bu₄N)₂[OsO₂(SeCN)₄] ( 3 ) (tetragonal, space group I4/m, a = 13.406(2), c = 12.871(1) Å, Z = 2) have been determined by single‐crystal X‐ray diffraction analysis, showing the bonding of NCO and NCS via the N atom but the coordination of SeCN via the Se atom to osmium. Based on the molecular parameters of the X‐ray determinations the vibrational spectra have been assigned by normal coordinate analyses. The valence force constants are for 1 f_d(OsO) = 6.43, f_d(OsN) = 3.32, f_d(NC) = 14.50, f_d(CO) = 12.80, for 2 f_d(OsO) = 6.56, f_d(OsN) = 1.75, f_d(NC) = 15.00, f_d(CS) = 5.50, and for 3 f_d(OsO) = 6.75, f_d(OsSe) = 0.99, f_d(SeC) = 3.23, f_d(CN) = 15.95 mdyn/Å. The observed NMR shifts are δ(¹⁵N) = –386.6 ( 1 ), δ(¹⁵N) = –294.7 ( 2 ) and δ(⁷⁷Se) = 108.8 ppm ( 3 ).     

Darstellung,Kristallstrukturen und Schwingungsspektren von bindungsisomeren Pentabromorhodanoosmaten(IV)

Synthesis, Crystal Structures and Vibrational Spectra of Linkage Isomeric Pentabromorhodanoosmates(IV) By treatment of (n‐Bu₄N)₂[OsBr₅I] with (SCN)₂ in dichloromethane the linkage isomers (n‐Bu₄N)₂[OsBr₅(NCS)] and (n‐Bu₄N)₂[OsBr₅(SCN)] are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[OsBr₅(NCS)] (monoclinic, space group P2₁/n, a = 10.955(5), b = 11.649(5), c = 35.478(5) Å, β = 91.92(1)°, Z = 4) and (CH₂Py₂)[OsBr₅(SCN)] (monoclinic, space group P2₁/n, a = 12.244(2), b = 10.134(3), c = 15.882(4) Å, β = 107.91(2)°, Z = 4) have been performed. The thiocyanate group is coordinated with the Os–N–C angle of 168° for N bonding and the Os–S–C angle of 110° for S bonding. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra of both linkage isomers are assigned by normal coordinate analysis. The valence force constants are f_d(OsN) = 1,81 and f_d(OsS) = 1,42 mdyn/Å.     

Darstellung,Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von (Ph4P)2[OsN(N3)5] und 15N‐NMR‐Verschiebungen von Nitridoosmaten(VI,VIII)

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of (Ph₄P)₂[OsN(N₃)₅] and ¹⁵N NMR Chemical Shifts of Nitridoosmates(VI, VIII) The treatment of (Ph₄P)[OsNCl₄] with NaN₃ yields (Ph₄P)₂[OsN(N₃)₅], which crystal structure has been determined by single crystal X‐ray diffraction analysis (monoclinic, space group P 2₁/a, a = 20.484(6), b = 11.168(1), c = 20.666(4) Å, β = 97.35(3)°, Z = 4). The IR and Raman vibrations were assigned by a normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(Os≡N) = 8.52, f_d(Os–N^α) = 1.99, f_d(N^α–N^β) = 12.42, f_d(N^β–N^γ) = 12.73 and for the azido ligand in trans‐position to the nitrido group f_d(Os–N^{α ·} ) = 1.84, f_d(N^{α ·} –N^{β ·} ) = 11.91, f_d(N^{β ·} –N^{γ ·} ) = 12.18 mdyn/Å. The ¹⁵N NMR spectra of various nitridoosmates reveal the chemical shifts δ(¹⁵N) for K[OsO₃¹⁵N] = 387.6, K₂[Os¹⁵NCl₅] = 446.7, (Ph₄P)[Os¹⁵NCl₄] = 352.9, [(n‐C₆H₁₃)₄N]₂[Os¹⁵N(N₃)₅] = 307.3 and for [(n‐Pr)₄N]₂[Os¹⁵N(¹⁵NCO)₅] = 483,7 (Os≡N), –417,7 (OsNCO_eq) und –392,8 ppm (OsNCO_ax).     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen der mer‐Trihalogeno‐tris‐Pyridin‐Osmium(III)Komplexe mer‐[OsX3Py3], X = Cl,Br, I

Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the mer ‐Trihalogeno‐tris‐Pyridine‐Osmium(III) Complexes mer‐[OsX₃Py₃], X = Cl, Br, I By reaction of the hexahalogenoosmates(IV) with pyridine and iso‐amylalcohol mer‐trihalogeno‐tris‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of mer‐[OsBr₃Py₃] (monoclinic, space group P2₁/n, a = 9.098(5), b = 12.864(5), c = 15.632(5) Å, β = 90.216(5)°, Z = 4) and mer‐[OsI₃Py₃] (monoclinic, space group P2₁/n, a = 9.0952(17), b = 13.461(4), c = 15.891(10), β = 91.569(5)°, Z = 4). The pyridine rings are twisted propeller‐like against the N₃ meridional plane with mean angles of 49° (Cl), 46° (Br), 44° (I). Based on the molecular parameters of the X‐ray structure determinations and assuming C₂ point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis. Due to the stronger trans influence of pyridine as compared with the halide ligands for N'–Os–X ^· axes significantly different valence force constants are observed in comparison with symmetrically coordinated octahedron axes: f_d(OsCl) = 1.74, f_d(OsCl^·) = 1.49, f_d(OsBr) = 1.43, f_d(OsBr ^· ) = 1.18, f_d(OsI) = 0.99, f_d(OsI ^· ) = 0.96, f_d(OsN) between 1.96 and 2.07 and f_d(OsN') between 2.13 and 2.32 mdyn/Å.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von (n‐Bu4N)2[PtX4(ox)], X = Cl,BR

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of (n‐Bu₄N)₂[PtX₄(ox)], X = Cl, Br By oxidation of (n‐Bu₄N)₂[PtX₂(ox)], X = Cl, Br, with Cl₂ or Br₂ in dichloromethane (n‐Bu₄N)₂[PtCl₄(ox)] ( 1 ) and (n‐Bu₄N)₂[PtBr₄(ox)] ( 2 ) are formed. The crystal structure of [(C₅H₅N)₂CH₂][PtCl₄(ox)] (monoclinic, space group C2/m, a = 15.562(1), b = 13.779(1), c = 10.168(1)Å, ß = 128.099(9)°, Z = 4) reveals complex anions with nearly C_2v point symmetry. The bond lengths in the Cl′‐Pt‐O^˙ axes are Pt‐Cl′ = 2.287 and Pt‐O^˙ = 2.048 and in the Cl‐Pt‐Cl axis Pt‐Cl = 2.314Å. The oxalato ligand is nearly plane with an O‐C‐C‐O torsion angle of 0.5°. In the vibrational spectra the PtX stretching vibrations are observed at 328 and 353 ( 1 ) and 201 and 212 cm^—1 ( 2 ). The PtX′ modes appear at 360 and 343 ( 1 ) and 227 and 238 cm^—1 ( 2 ). The PtO^˙ stretching vibrations are coupled with internal modes of the oxalato ligands and appear in the range of 400—800 cm^—1. Based on the molecular parameters of the X‐ray determination ( 1 ) and estimated data ( 2 ) the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtCl) = 2.08, f_d(PtCl′) = 2.29, f_d(PtBr) = 1.56, f_d(PtBr′) = 2.02 and f_d(PtO^˙) = 2.46 ( 1 ) and 2.35 mdyn/Å ( 2 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(¹⁹⁵Pt) = 5623.0 ( 1 ) and 4536.1 ( 2 ).     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen von trans-(PNP)[TcCl4(Py)2] und trans-(PNP)[TcBr4(Py)2]

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of trans-(PNP)[TcCl₄(Py)₂] and trans-(PNP)[TcBr₄(Py)₂] By reaction of (PNP)₂[TcX₆] with pyridine in the presence of [BH₄]^? (PNP)[TcX₄(Py)₂], X = Cl, Br, are formed. X-ray structure determinations on single crystals of these isotypic Tc^III complexes (monoclinic, space group P2₁/n, Z = 2, for X = Cl: a = 13.676(4), b = 9.102(3), c = 17.144(2) Å, β = 91.159(1)°; for X = Br: a = 13.972(2), b = 9.146(3), c = 17.285(4) Å, β = 90.789(2)°) result in the averaged bond distances Tc? Cl: 2.386, Tc? Br: 2.519, Tc? N: 2.132(3) (X = Cl) and 2.143(4) Å (X = Br). The two pyridine rings are coplanar and vertical to the X? Tc? X-axes, forming angles of 42.28° (X = Cl) and 43.11° (X = Br). Using the molecular parameters of the X-ray structure determination and assuming D_2h point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis based on a modified valence force field. Good agreement between observed and calculated frequencies is obtained with the valence force constants f_d(TcCl) = 1.45, f_d(TcBr) = 1.035, f_d(TcN) = 1.37 (X = Cl) and 1.45 mdyn/ Å (X = Br), respectively.     

Darstellung und Kristallstrukturen von (Ph3PNPPh3)2[Re2Br10] und (Ph4P)[Re2Br9]

Synthesis and Crystal Structures of (Ph₃PNPPh₃)₂[Re₂Br₁₀] and (Ph₄P)[Re₂Br₉] Depending on the molar ratio by reaction of [n-Bu₄N]₂[ReBr₆] with the Lewis acid BBr₃ in dichloromethane the bioctahedral complexes [n-Bu₄N]₂[Re₂Br₁₀] and [n-Bu₄N][Re₂Br₉] are formed. The X-ray structure determination on (Ph₃PNPPh₃)₂[Re₂Br₁₀] (monoclinic, space group C 2/c, a = 20.007(4), b = 15.456(5), c = 24.695(4) Å, β = 107.53(2)°, Z = 4) reveals a centrosymmetric edge-sharing complex anion with approximate D_2h symmetry and mean terminal and bridging Re–Br bond lengths of 2.453 (equatorial), 2.482 (axial) and 2.591 Å, respectively, and a Re–Re distance of 3.880 Å. (Ph₄P)[Re₂Br₉] (triclinic, space group P 1, a = 11.062(2), b = 12.430(3), c = 13.163(5) Å, α = 72.94(2), β = 68.47(2), γ = 82.09(2)°, Z = 2) contains a confacial bioctahedral anion with nearly D_3h symmetry and mean terminal and bridging Re–Br distances of 2.460 and 2.536 Å, respectively, and a Re–Re distance of 2.780 Å.     

Kristallstruktur,Schwingungsspektrum und Normalkoordinatenanalyse von (PNP)2[ReFBr5] · H2O

Crystal Structure, Vibrational Spectrum, and Normal Coordinate Analysis of (PNP)₂[ReFBr₅] · H₂O From the complex mixture obtained by oxidative ligand exchange of [ReBr₆]^2– with BrF₃ [ReFBr₅]^2– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose with 45% yield. The X-ray structure determination of (PNP)₂[ReFBr₅] · H₂O (monoclinic, space group P2₁/c with a = 21.498(2), b = 13.314(3), c = 23.945(2) Å, β = 105.235(7)°, Z = 4) reveals a completely ordered anion sublattice resulting from the solvent water linked to the F ligand by a hydrogen bond (O–F: 2.758(6) Å). Due to the stronger trans influence of Br compared with F on the F ^· –Re–Br′ axis the Re–Br′ distance is shortened by 0.6% with regard to symmetrically coordinated axes. Based on the molecular parameters of the X-Ray determination the low temperature (10 K) IR and Raman spectrum of the (Me₄N) salt is assigned by a normal coordinate analysis. The strengthening of the Re–Br′ bond due to the trans influence is indicated by an increase of the valence force constant f_d(ReBr′) = 1.43 by 8% as compared with f_d(ReBr) = 1.32 mdyn/Å of symmetric axes.