Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse der bindungsisomeren Chlororhodanoiridate(III) trans-[IrCl2(SCN)4]3− und trans-[IrCl2(NCS)(SCN)3]3−

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of the Linkage Isomeric Chlororhodanoiridates(III) trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? By treatment of Na₂[IrCl₆] with NaSCN in 2N HCl the linkage isomers trans-[IrCl₂(SCN)₄]^3? and trans-[IrCl₂(NCS)(SCN)₃]^3? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations on single crystals of trans-(n-Bu₄N)₃[IrCl₂(SCN)₄] ( 1 ) (monoclinic, space group P2₁/a, a = 18.009(4), b = 15.176(3), c = 23.451(4) Å, β = 93.97(2)°, Z = 4) and trans-(Me₄N)₃[IrCl₂(NCS)(SCN)₃] ( 2 ) (monoclinic, space group P2₁/a, a = 17.146(5), b = 9.583(5), c = 18.516(5) Å, β = 109.227(5)°, Z = 4) reveal the complete ordering of the complex anions. The via S or N coordinated thiocyanate groups are bonded with Ir? S? C angles of 105.7–109.7° and the Ir? N? C angle of 171.4°. The torsion angles Cl? Ir? S? C and N? Ir? S? C are 3.6–53.0°. The IR and Raman spectra of ( 1 ) are assigned by normal coordinate analysis using the molecular parameters of the X-ray determination. The valence force constants are f_d(IrS) = 1.52 and f_d(IrCl) = 1.72 mdyn/Å.     

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 von (Me4N)3[Ir(SCN)6], Schwingungsspektrum und Normalkoordinatenanalyse

Crystal Structure of (Me₄N)₃[Ir(SCN)₆], Vibrational Spectra and Normal Coordinate Analysis From a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6–n]^3–, n = 0–2, pure [Ir(SCN)₆]^3– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of (Me₄N)₃[Ir(SCN)₆] (trigonal, space group R3, a = 14.838(2), c = 23.827(1) Å, Z = 6) reveals the presence of two crystallographically independent complex anions which C_3i symmetry correlates with the cation/anion ratio 3 : 1. The thiocyanate ligands are exclusively S-coordinated with the average Ir–S distance of 2.384 Å and the Ir–S–C angle of 106.4°. The torsion angles S–Ir–S–C are 17.5 and 42.1°. The IR and Raman spectra of the (n-Bu₄N) salt are assigned by normal coordinate analysis based on the molecular parameters of the X-ray determination. The valence force constant f_d(IrS) is 1.57 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 und Kristallstruktur von Tetraphenylphosphonium-Hexathiocyanatorhodat(III), [P(C6H5)4]3[Rh(SCN)6]

Preparation and Crystal Structure of Tetraphenylphosphonium Hexathiocyanatorhodate(III), [P(C₆H₅)₄]₃[Rh(SCN)₆] By treatment of RhCl₃ · n H₂O with KSCN in water a mixture of the linkage isomers [Rh(NCS)_n(SCN)_6–n]^3?, n = 0–2 is formed which is separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of [P(C₆H₅)₄]₃[Rh(SCN)₆] (monoclinic, space group C1c1, a = 13.620(5), b = 22.929(13), c = 22.899(9) Å, β = 98.55(3)°, Z = 4) confirms the coordination of all ligands via S with the middle Rh? S distance of 2.372 Å and Rh? S? C angles of 109°. The SCN groups are nearly linear with 175° and averaged bondlengths S? C 1.63 and C? N 1.14 Å. The crystal lattice is build up by layers of complex anions and voluminous cations with no specific interactions but which are closely connected by thiocyanate ligands and phenyl rings.     

Darstellung,Schwingungsspektren und Normalkoordinatenanalyse von mer-[OsCl3I(NCS)]2− sowie Kristallstrukturanalyse von zwei Modifikationen des mer-(Ph4As)2[OsCl3I(NCS)2c]

Preparation, Vibrational Spectra, and Normal Cooordinate Analysis of mer-[OsCl₃I(NCS)₂^c]^2? and Crystal Structures of two Modifications of mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] By treatment of cis-/trans-[OsCl₄I₂]^2? or fac-[OsCl₃I₃]^2? with (SCN)₂ in dichloromethane mixtures of different linkage isomers are formed, from which mer-[OsCl₃I(NCS)]^2? has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. With tetraphenylarsonium ions mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] crystallizes in two different modifications. From acetone solution the high-temperature form α precipitates above ?10°C, the low-temperature form β below, ?65°C. The X-Ray structure determinations on single crystals of α-mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] (triclinic, space group P 1 , a = 10.245(5), b = 11.690(5), c = 22.027(5) Å, α = 83.650(5)°, β = 85.734(5)°, γ = 72.566(5)°, Z = 2) and β-mer-(Ph₄As)₂[OsCl₃I(NCS)₂^c] (triclinic, space group P 1 , a = 10.959(5), b = 11.122(5), c = 21.745(5) Å, α = 97.677(5)°, β = 92.339(5)°, γ = 104.712(5)°, Z = 2) reveal the ordering of the complex anions, which significantly differ in their geometry. The via N coordinated thiocyanate groups exhibit Os? N? C angles of 172.7° and 173.3° (α) and of 164.4° and 175.4° (β). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salt of the complex anion are assigned by a normal coordinate analysis based on a modified valence force field. The valence force constants are f_d(OsN) = 1.66 and 1.64 mdyn/Å. Taking into account the trans influence a good agreement between observed and calculated frequencies is achieved.     

Darstellung und Kristallstruktur von trans-(Ph4As)2[OsCl2(NCS)(SCN)], Schwingungsspektren und Normalkoordinatenanalyse

Preparation and Crystal Structure of trans-(Ph₄As)₂[OsCl₂(NCS) (SCN) ], Vibrational Spectra and Normal Coordinate Analysis By treatment of trans-[OsCl₂I₄]^2? with (SCN)₂ in dichloromethane a mixture of different linkage isomers is formed, from which trans-[OsCl₂(NCS)(SCN)]^2? has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determination on a single crystal of trans-(Ph₄As)₂[OsCl₂(NCS)(SCN)] (triclinic, space group P 1 , a = 12.505(5), b = 12.056(5), c = 19.833(5) Å, α = 108.047(5)°, β = 91.964(5)°, γ = 117.048(5)°, Z = 2) reveals that two cis-positioned Thiocyanate(N) groups are coordinated with Os? N? C angles of 172.1° and 173.0° and two cis-positioned Thiocyanate(S) groups are coordinated with Os? S? C angles of 106.9° and 108.7°. Using the molecular parameters of the X-Ray determination the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salt of the linkage isomer are assigned by a normal coordinate analysis based on a modified valence force field. The valence force constants are f_d(OsN) = 1.63 and f_d(OsS) = 1.30 mdyn/Å. Taking into account the trans influence a good agreement between observed and calculated frequencies is achieved.     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalyse von (n‐Bu4N)2[Os(NCS)6] und (n‐Bu4N)3[Os(NCS)6]

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[Os(NCS)₆] and ( n ‐Bu₄N)₃[Os(NCS)₆] By tempering the solid mixture of the linkage isomers (n‐Bu₄N)₃[Os(NCS)_n(SCN)_6–n] n = 0–5 for a longer time at temperatures increasing from 60 to 140 °C the homoleptic (n‐Bu₄N)₃[Os(NCS)₆] is formed, which on oxidation with (NH₄)₂[Ce(NO₃)₆] in acetone yields the corresponding Os^IV complex (n‐Bu₄N)₂[Os(NCS)₆]. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Os(NCS)₆] (1) (triclinic, space group P 1, a = 12.596(5), b = 12.666(5), c = 16.026(5) Å, α = 88.063(5), β = 80.439(5), γ = 88.637(5)°, Z = 2) and (n‐Bu₄N)₃[Os(NCS)₆] ( 2 ) (cubic, space group Pa 3, a = 24.349(4) Å, Z = 8) have been performed. The nearly linear thiocyanate groups are coordinated with Os–N–C angles of 172.3–177.7°. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constant f_d(OsN) is 2.3 ( 1 ) and 2.10 mdyn/Å ( 2 ).     

Darstellung,Kristallstruktur und Normalkoordinatenanalyse der bindungsisomeren Pentachlororhodanoosmate(IV)

Preparation, Crystal Structure and Normal Coordinate Analysis of Linkage Isomeric Pentachlororhodanoosmates(IV) By treatment of [OsCl₅I]^2? with (SCN)₂ in dichloromethane the linkage isomers [OsCl₅(NCS)]^2? and [OsCl₅(SCN)]^2? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (Ph₄As)₂[OsCl₅(NCS)] (monoclinic, space group P2₁/a, a = 18.872(2), b = 11.6024(2), c = 22.786(1), β = 109.057(1)°, Z = 4) and (Ph₄As)₂[OsCl₅(SCN)] (monoclinic, space group P2₁/a, a = 19.057(2), b = 11.306(2), c = 22.612(1), β = 106.64(2)°, Z = 4) reveals the complete ordering of the complex anions. The thiocyanate group is located above one of the Cl ligands of the equatorial plane with the Os? N? C angle of 166.1° for N bonding and the Os? S? C angle of 109.9° for S bonding. The IR and Raman spectra of both linkage isomers known from literature are assigned by normal coordinate analysis based on the general valence force field using the molecular parameters of the X-ray determination. The valence force constants are f_d(OsN) = 1,81 and f_d(OsS) = 1,32 mdyn/Å. Taking into account increments of the trans influence a good adjustment between observed and calculated frequencies is achieved.     

Kristallstruktur von Tetraphenylphosphonium-Monothiocyanatohydro-closo-Decaborat, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN

Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN The X-ray structure determination of [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN (monoclinic, space group P2₁/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°).     

Synthesis and Crystal Structures of Bis(tetraethylammonium)(2-oxo-1,3-dithiole-4,5-dithiolato)zincate(II) and Bis(tetra-n-butylammonium)(2-oxo-1,3-dithiole-4,5-dithiolato)zincate(II)

The title compounds were prepared from 1,3,4,6-tetrathiapentalene-2,5-dione ( 1 ) in one step via the in situ generated intermediate 2-oxo-1,3-dithiole-4,5-dithiolate (dmid; 2 ). The X-ray single crystal structure of (Et₄N)₂[Zn(dmid)₂] ( 3 a ) gave the tetragonal space group P4₃2₁2 with a = b = 13.810(2) Å, c = 16.480(3) Å, and Z = 4. (n-Bu₄N)₂[Zn(dmid)₂] ( 3 b ) gave the triclinic space group P 1 with a = 11.947(4) Å, b = 14.665(5) Å, c = 16.662(8) Å, α = 100.21(3)°, β = 104.46(3)°, γ = 110.73(3)°, and Z = 2.     

Darstellung,Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von [Co(NH3)6][Os(SCN)6]

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of [Co(NH₃)₆][Os(SCN)₆] From the mixture of the linkage isomers [Os(NCS)_n(SCN)_6–n]^3–, n = 0–2, pure [Os(SCN)₆]^3– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of [Co(NH₃)₆][Os(SCN)₆] (trigonal, space group R 3, a = 12.368(2), c = 11.830(2) Å, Z = 3) reveals that the thiocyanate ligands are exclusively S‐coordinated with the Os–S distance of 2.388 Å and the Os–S–C angle of 108.8°. The IR and Raman spectra of (n‐Bu₄N)₃[Os(SCN)₆] are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constant f_d(OsS) is 1.42 mdyn/Å.     

Darstellung und Strukturen von (Et4N)2[Re(CO)3(NCS)3] und (Et4N)[Re(CO)2Br4]

Syntheses and Structures of (Et₄N)₂[Re(CO)₃(NCS)₃] and (Et₄N)[Re(CO)₂Br₄] Rhenium(I) and rhenium(III) carbonyl complexes can easily be prepared by ligand exchange reactions starting from (Et₄N)₂[Re(CO)₃Br₃]. Using nonoxidizing reagents the facial Re^I(CO)₃ unit remains and only the bromo ligands are exchanged. Following this procedure, (Et₄N)₂[Re(CO)₃(NCS)₃] can be obtained in high yield and purity using trimethylsilylisothiocyanate. The compound crystallizes in the monoclinic space group P2₁/n, a = 18.442(5), b = 17.724(3), c = 18.668(5) Å, β = 92.54(1)°, Z = 8. The NCS^? ligands are coordinated via nitrogen. The reaction of [Re(CO)₃Br₃]^2? with Br₂ yields the rhenium(III) anion [Re(CO)₂Br₄]^?. The tetraethylammonium salt of this complex crystallizes in the noncentrosymmetric, orthorhombic space group Cmc2₁, a = 8.311(1), b = 25.480(6), c = 8.624(1) Å, Z = 4. The carbonyl ligands are positioned in a cis arrangement. Their strong trans influence causes a lengthening of the Re? Br bond distances by at least 0.05 Å.     

31P-NMR and X-Ray Studies of the Complexes [HgX2 (1)]. (1=2, 11-bis (diphenylphosphinomethyl)benzo [c]phenanthrene,X=Cl,I)

The ³¹P{¹H}-NMR characteristics of the complexes [HgX₂( 1 )] and [HgX₂-(PPh₂Bz)₂] (X = NO₃, Cl, Br, I, SCN, CN) and the solid state structures of the complexes [HgCl₂( 1 )] and [HgI₂( 1 )] ( 1 = 2,11-bis (diphenylphosphinomethyl)benzo-[c]phenanthrene) have been determined. The ¹J(¹⁹⁹Hg, ³¹P) values increase in the order CN < I < SCN < Br < Cl < NO₃. The two molecular structures show a distorted tetrahedral geometry about mercury. Pertinent bond lengths and bond angles from the X-ray analysis are as follows: Hg? P = 2.485(7) Å and 2.509 (8) Å, Hg? Cl = 2.525 (8) Å and 2.505 (10) Å, P? Hg? P = 125.6(3)°, Cl? Hg? Cl = 97.0(3)° for [HgCl₂( 1 )] and Hg? P = 2.491 (10) Å and 2.500(11) Å, Hg? I = 2.858(5) Å and 2.832(3) Å, P? Hg? P = 146.0(4)°, I? Hg? I = 116.9(1)° for [HgI₂( 1 )]. The equation, derived previously, relating ¹J(¹⁹⁹Hg, ³¹P) and the angles P? Hg? P and X? Hg? X is shown to be valid for 1 .     

Darstellung,Kristallstruktur und Schwingungsspektren von (n-Bu4N)2[(Mo6I)(NCS)]

Synthesis, Crystal Structure, and Vibrational Spectra of (n-Bu₄N)₂[(Mo₆I)(NCS)] By treatment of [(Mo₆I)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(Mo₆I)(NCS)]^2– is formed. The X-ray structure determination of (n-Bu₄N)₂[(Mo₆I)(NCS)] · 2 Me₂CO (monoclinic, space group P2₁/c, a = 13.168(5), b = 11.964(5), c = 24.636(5) Å, β = 104.960(5)°, Z = 2) shows, that the thiocyanate groups are coordinated exclusively via N atoms with Mo–N bond lengths of 2.141–2.150 Å, Mo–N–C angles of 166–178° and N–C–S-angles of 174–180°. The vibrational spectra exhibit characteristic innerligand vibrations at 2073–2054 (ν_CN), 846–844 (ν_CS) and 480–462 cm^–1 (δ_NCS).     

Kristallstrukturen,spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n‐Bu4N)2[M(ECN)4] (M = Pd,Pt; E = S,Se)

Crystal Structures, Spectroscopic Analysis, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[M(ECN)₄] (M = Pd, Pt; E = S, Se) The reaction of (NH₄)₂[PdCl₄] or K₂[PtCl₄] with KSCN or KSeCN in aqueous solutions yields the complex anions [Pd(SCN)₄]^2–, [Pt(SCN)₄]^2– and [Pt(SeCN)₄]^2–, which are converted into (n‐Bu₄N) salts with (n‐Bu₄N)HSO₄. (n‐Bu₄N)₂[Pd(SeCN)₄] is formed by treatment of (n‐Bu₄N)₂[PdCl₄] with (n‐Bu₄N)SeCN in acetone. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Pd(SCN)₄] (monoclinic, space group P2₁/n, a = 13.088(3), b = 12.481(2), c = 13.574(3) Å, β = 91.494(15)°, Z = 2), (n‐Bu₄N)₂[Pd(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.171(2), b = 12.644(2), c = 13.560(2) Å, β = 91.430(11)°, Z = 2) and (n‐Bu₄N)₂[Pt(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.167(2), b = 12.641(1), c = 13.563(2) Å, β = 91.516(18)°, Z = 2) reveal, that the compounds crystallize isotypically and the complex anions are centrosymmetric and approximate planar. In the Raman spectra the metal ligand stretching modes of (n‐Bu₄N)₂[Pd(SCN)₄] ( 1 ) and (n‐Bu₄N)₂[Pt(SCN)₄] ( 3 ) are observed in the range of 260–303 cm^–1 and of (n‐Bu₄N)₂[Pd(SeCN)₄] ( 2 ) and (n‐Bu₄N)₂[Pt(SeCN)₄] ( 4 ) in the range of 171–195 cm^–1. The IR and Raman spectra are assigned by normal coordinate analysis using the molecular parameters of the X‐ray determination. The valence force constants are f_d(PdS) = 1.17, f_d(PdSe) = 1.17, f_d(PtS) = 1.44 and f_d(PtSe) = 1.42 mdyn/Å. The ⁷⁷Se NMR resonances are 23 for 2 , –3 for 4 and the ¹⁹⁵Pt NMR resonances 549 for 3 and 130 ppm for 4 .     

Synthese und spektroskopische Charakterisierung von [Rh(SeCN)6]3– und trans‐[Rh(CN)2(SeCN)4]3–, Kristallstruktur von (Me4N)3[Rh(SeCN)6]

Synthesis and Spectroscopic Characterization of [Rh(SeCN)₆]^3– and trans ‐[Rh(CN)₂(SeCN)₄]^3–, Crystal Structure of (Me₄N)₃[Rh(SeCN)₆] Treatment of RhCl₃ with KSeCN in acetone yields a mixture of selenocyanato‐rhodates(III), from which [Rh(SeCN)₆]^3– and trans‐[Rh(CN)₂(SeCN)₄]^3– have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of (Me₄N)₃[Rh(SeCN)₆] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) Å, Z = 6) reveals, that the compound crystallizes isotypically to (Me₄N)₃[Ir(SCN)₆]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh–Se distance of 2.490 Å and the Rh–Se–C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes ν(RhSe) of (n‐Bu₄N)₃[Rh(SeCN)₆] ( 1 ) and trans‐(n‐Bu₄N)₃[Rh(CN)₂(SeCN)₄] ( 2 ) are in the range of 170–250 cm^–1. In 2 ν_as(CRhC) is observed at 479 cm^–1. The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(RhSe) = 1.08 ( 1 ), 1.10 ( 2 ) and f_d(RhC) = 3.14 mdyn/Å ( 2 ). f_d(RhS) = 1.32 mdyn/Å is determined for [Rh(SCN)₆]^3–, which has not been calculated so far. The ¹⁰³Rh NMR resonances are 2287 ( 1 ), 1680 ppm ( 2 ) and the ⁷⁷Se NMR resonances are –32.7 ( 1 ) and –110.7 ppm ( 2 ). The Rh–C bonding of the cyano ligand in 2 is confirmed by a dublett in the ¹³C NMR spectrum at 136.3 ppm.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von [(Mo6Br)Y]2−; Ya  CN,NCS

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of [(Mo₆Br )Y ]^2?; Y^a ? CN, NCS By treatment of [(Mo₆Br)Br^a₆]^2? with AgNO₃ in acetone and addition of KCN or KNCS the hexacyano and hexaisothiocyanato derivates [(Mo₆Br)Y]^2?, Y^a ? CN, NCS are formed. X-ray structure determinations of (Ph₄P)₂ [(Mo₆Br)(CN)^a₆]·4H₂ O ( 1 ) (triclinic, spacegroup P1, a = 11.63(3), b = 11.85(1), c = 14.23(5) Å, α = 71.8(1)°, β = 67.6(3)°, γ = 62.8(1)°, Z= 1) and (n-Bu₄N)₂[(Mo₆Br ⁱ₈)(NCS)^a₆] · 2Et₂O ( 2 ) (monoclinic, spacegroup P2₁/n, a = 11.483(3), b = 16.348(5), c = 20.059(6) Å, β= 95.44(3)°, Z = 2) have been performed. The via C coordinated cyano ligands of ( 1 ) reveal facial groups with (MoCN) angles of 168.0–171,5° and 174.1°–175.7°. In ( 2 ) the via N coordinated isothiocyanato groups at the apical positions show MoNC-angles of 164.4°, the equatorial angles are 172.7–173.5°. Using the molecular parameters of the X-ray determinations the 10 K IR and Raman spectra of the (n-Bu₄N) cluster salts are assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(MoMo) = 1.41 (CN^a), 1.43 (NCS^a), f_d (MoBrⁱ) = 0.97 (CN^a), 0.96 (NCS^a), f_d(MoC) = 1.62, f_d(Mo-N) = 2.09 mdyne/Å.     

Chalkogenohalogenogallate(III) und -indate(III): Eine neue Verbindungsklasse in der dritten Hauptgruppe. Synthese und Struktur von [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN und [Et4N]3[Ga3S3Cl6] · THF (X = Cl,Br; E = S,Se)

Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph₄P]₂[In₂SX₆], [Et₄N]₃[In₃E₃Cl₆] · MeCN and [Et₄N]₃[Ga₃S₃Cl₆] · THF (X = Cl, Br; E = S, Se) [In₂SCl₆]^2?, [In₂SBr₆]^2?, [In₃S₃Cl₆]^3?, [In₃Se₃Cl₆]^3?, and [Ga₃S₃Cl₆]^3? were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph₄P]₂[In₂SCl₆] ( 1 ) (P1 ; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph₄P]₂[In₂SBr₆] ( 2 ) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX₃, (CH₃)₃SiSSi(CH₃)₃ and Ph₄PX (X = Cl, Br) in acetonitrile. The reaction of MCl₃ (M = Ga, In) with Et₄NSH/Et₄NSeH in acetonitrile gave [Et₄N]₃[In₃S₃Cl₆] · MeCN ( 3 ) (P2₁/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et₄N]₃[In₃Se₃Cl₆] · MeCN ( 4 ) (P2₁/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et₄N]₃[Ga₃S₃Cl₆] · THF ( 5 ) (P2₁/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In₂SX₆]^2? anions (X = Cl, Br) in 1 and 2 consist of two InSX₃ tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.     

Neue dimere Goldselenolate: Darstellung und strukturelle Charakterisierung von [(n-C4H9)4N]2[AuSSeCC(CN)2]2 und [(n-C4H9)4N]2[AuSe2CC(CN)2]2

New Dimeric Gold Selenolates: Preparation and Characterization of [(n-C₄H₉)₄N]₂[AuSSeC ? C(CN)₂]₂ and [(n-C₄H₉)₄N]₂[AuSe₂C ? C(CN)₂]₂ The preparation and structural characterization of the dimeric Au^I complexes of 1,1-dicyanoethene-2,2-thioseleonlate (i-mnts) and 1,1-dicyanoethene-2,2-diselenolate (i-mns), isolated as Bu₄N salts, are described. They are isotype (monoclinic, space group P2₁/c, Z = 2) with lattice parameters: (Bu₄N)₂[Au(i-mnts)]₂; a = 14.078(3) Å, b = 8.912(3) Å, c = 20.142(4) Å, β = 106.32(5)°; (Bu₄N)₂[Au(i-mns)]₂; a = 13.998(3) Å, b = 9.125(3) Å, c = 20.039(2) Å, β = 105.12(5)°. Ab initio Hartree-Fock calculations based on the experimentally determined structure yield a positive value of the Au? Au bonding order suggesting weak bonding interactions between the d¹⁰ metal centres.