Synthesis and comprehensive characterizations of new cis-RuL(2)X(2) (X = Cl, CN, and NCS) sensitizers for nanocrystalline TiO(2) solar cell using Bis-phosphonated bipyridine ligands (L)

The preparation and the properties of several ruthenium complexes of the general formula cis-RuL(2)X(2) with L = 2,2'-bipyridine-4,4'-bisphosphonic acid, L' = 2,2'-bipyridine-5,5'-bisphosphonic acid, and X = Cl, CN, or NCS are reported. The synthesis of these complexes relies on the preparation of the key intermediates cis-Ru(bipyridinebis(diethyl ester phosphonate))Cl(2). The ground-state second pK(a) values of the thiocyanato complexes were determined and are 6.0 and 6.1 for cis-RuL(2)(NCS)(2) and for cis-RuL'(2)(NCS)(2), respectively. For these species, (13)C NMR and IR demonstrate that the thiocyanato ligands are bound to Ru via the N atom. The new complexes exhibit a blue-shifted electronic absorption spectrum with respect to the analogous complexes containing carboxylic acid groups. Density functional theory molecular orbital calculations show that the LUMO of the bipyridine phosphonated ligands is at higher energy than the corresponding dicarboxylate complexes and that the thiocyanato ligands are not simple spectator ligands, whose role is to enrich electron density on the ruthenium, but are also involved in transitions from PiRu-NCS to Pibpy that extend the absorbance of the dye in the low energy part of the absorption spectrum. The photoaction spectra recorded in a sandwich regenerative photovoltaic cell indicate that the cyano and thiocyanato complexes containing the bipyridine substituted in 4,4' positions exhibit a 90-95% photoconversion efficiency on the MLCT band, whereas those containing the bipyridine substituted in 5,5' positions display lower efficiency (60-65%). The most efficient complex in the series is cis-RuL(2)(NCS)(2); however, its overall efficiency is about 30% lower than the analogue cis-Ru(H(2)dcb)(2)(NCS)(2) (H(2)dcb = 2,2'-bipyridine-4,4'-dicarboxylic acid) due to a lower absorbance in the red part of the visible spectrum.     

Über ternäre Pseudohalogeno-dicyanomercurate(II) MHg(CN)2X (M = Na,K, Rb,Cs; X = NCO,NCS und N3)

On the Ternary Pseudohalogeno-dicyanomercurates(II) MHg(CN)₂X (M = Na, K, Rb, Cs; X = NCO, NCS, N₃) The structures of the pseudohalogeno-dicyanomercurates MHg(CN)₂X · nH₂O, formed by reaction of Hg(CN)₂ with alkalipseudohalides MX (M = Na, K, Rb, Cs; X = NCO, NCS N₃) in aqueous solutions containing digonal Hg(CN)₂ molecules besides M⁺ and X^? anions. Therefore the compounds can be formulated as double salts MX · Hg(CN)₂. There are three types of structures with different values of crystal water whose structures have been determined by X-ray analysis of the cyanates NaHg(CN)₂OCN · 2H₂O, KHg (CN)₂OCN and CsHg(CN)₂OCN · H₂O.     

Reactions of nitrosyl chloride with [Ni(PPh3)2X2] (X=Cl,Br, NCS or NO3)

Summary Nitrosyl chloride has been treated with [Ni(PPh₃)₂X₂] (X = Cl, Br, NCS or NO₃) to obtain [Ni(PPh₃)XCl]₂ (X=Cl, Br, NCS or NO₃) and [Ni(OPPh₃)(SCN)Cl]₂. The compounds obtained were characterised by analyses, infrared (including far i.r.) and visible spectral studies, magnetic moment and conductivity measurements and many chemical reactions. It is proposed that the compounds have a dimeric structure with a distorted tetrahedral environment around the nickel atom and chloro-bridges.     

Ruthenium(II)-Phthalocyaninate(2–): Darstellung und Eigenschaften von Acido(carbonyl)phthalocyaninato(2–)ruthenat(II), [Ru(X)(CO)Pc2−]− (X = Cl,Br, I,NCO, NCS,N3)

Ruthenium(II) Phthalocyaninates(2–): Synthesis and Properties of (Acido)(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) (ⁿBu₄N)[Ru(OH)₂Pc^2?] is reduced in acetone with carbonmonoxid to blue-violet [Ru(H₂O)(CO)Pc^2?], which yields in tetrahydrofurane with excess (ⁿBu₄N)X acido(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) isolated as red-violet, diamagnetic (ⁿBu₄N) complex salt. The UV-Vis spectra are dominated by the typical π-π* transitions of the Pc^2? ligand at approximately 15100 (B), 28300 (Q₁) und 33500 cm^?1 (Q₂), only fairly dependent of the axial ligands. v(C? O) is observed at 1927 (X = I), 1930 (Cl, Br), 1936 (N₃, NCO) 1948 cm^?1 (NCS), v(C? N) at 2208 cm^?1 (NCO), 2093 cm^?1 (NCS) and v(N? N) at 2030 cm^?1 only in the MIR spectrum. v(Ru? C) coincides in the FIR spectrum with a deformation vibration of the Pc ligand, but is detected in the resonance Raman(RR) spectrum at 516 (X = Cl), 512 (Br), 510 (N₃), 504 (I), 499 (NCO), 498 cm^?1 (NCS). v(Ru? X) is observed in the FIR spectrum at 257 (X = Cl), 191 (Br), 166 (I), 349 (N₃), 336 (NCO) and 224 cm^?1 (NCS). Only v(Ru? I) is RR-enhanced.     

Synthesis and evaluation of dioxygen binding [Mn(depe)2X2] complexes (X=Br or NCS)

Summary Synthesis, characterization and oxygen affinity studies for [Mn(depe)₂X₂] [X=Br or NCS; depe=1,2-bis(diethylphosphino)ethane] complexes are reported. [Mn(depe)₂Br₂] crystals were obtained and characterized by single crystal x-ray and elemental analysis. Gravimetric and volumetric dioxygen uptake studies were performed at atmospheric pressure at various temperatures. These transition metal compounds show considerable dioxygen uptake at various partial pressures of dioxygen. Some isotherm and kinetic data for dioxygen coordination by these complexes at ambient pressures are presented.     

联吡啶钌配合物[Ru(Htcterpy)X3]3-[X=NCS,CN,Cl]的电子结构和光谱性质的理论研究

利用DFT中的B3LYP方法优化了3个联吡啶钌配合物[Ru(Htcterpy)X3]3-[tcterpy=4,4',4"-tricarboxy-2,2'∶6',2"-terpyridine, X=NCS(1), CN(2), Cl(3)]的基态几何结构, 得到的几何参数与实验结果吻合得很好. 采用TD-DFT方法, 得到了配合物1~3在气态和溶液(乙醇溶液和水溶液)中的激发态电子结构和电子吸收光谱. 利用SCRF方法中的CPCM模型来模拟溶剂化效应. 研究结果表明, 配合物1~3在气态和溶液中的吸收跃迁性质相似, 低能吸收均被指认为MLCT和LLCT的混合跃迁, 高能吸收均被指认为三联吡啶配体内的π→π*跃迁. 溶剂化效应使配合物1~3在溶液中的吸收光谱蓝移.     

HCHO+X(X=F、Cl、Br)的反应机理

采用CCSD/6-311++G(d,p)//B3LYP/6-311++G(d,p)方法研究了HCHO与卤素原子X(X=F、Cl、Br)的反应机理. 计算结果表明, 卤素原子X(X=F、Cl、Br)主要通过直接提取HCHO中的H原子生成HCO+HX(X=F、Cl、Br). 另外还可以生成稳定的中间体, 中间体再通过卤原子夺氢和氢原子直接解离两个反应通道分别生成HCO+HX(X=F、Cl、Br)和H+XCHO(X=F、Cl、Br). 其中卤原子夺氢通道为主反应通道, HCO和HX(X=F、Cl、Br)为主要的反应产物; 且三个反应的活化能均较低, 说明此类反应很容易进行, 计算结果与实验结果符合很好. 电子密度拓扑分析显示, 在HCHO+X反应通道(b)中出现了T型结构过渡态, 结构过渡态(STS)位于能量过渡态(ETS)之后. 并且按F、Cl、Br的顺序, 结构过渡态出现得越来越晚.     

Effect of Ligand Field Strength on the Spin Crossover Behaviour in 5‐X‐SalEen (X=Me,Br and OMe) Based Fe(III) Complexes

The reaction of Fe(NCS)₃ prepared in situ in MeOH with 5‐X‐SalEen ligands (5‐X‐SalEen=condensation product of 5‐substituted salicylaldehyde and N‐ethylethylenediamine) provided three Fe(III) complexes, [Fe(5‐X‐SalEen)₂]NCS; X=Me ( 1 ), X=Br ( 2 ), X=OMe ( 3 ). All the complexes reveal similar structural features but a very different magnetic profile. Complex 1 shows a gradual spin crossover while complexes 2 and 3 show a sharp spin transition. The T_1/2 for complex 2 is 237 K while for complex 3 it is much higher with a value of 361 K. The spin transition temperature is shifted towards higher temperature with increasing electron‐donation ability of the ligand substituents. This experimental observation has been rationalized with DFT calculations. UV‐Vis and cyclic voltammetry studies support the fact that the electron density on the ligand increases from Me to Br to OMe substituents. To understand the change in spin states, temperature‐dependent EPR spectra have been recorded. The spin state equilibrium in the liquid state has been probed with Evans NMR spectroscopic method, and thermodynamic parameters have been evaluated for all complexes.     

过渡金属氢化物和聚集双键化合物反应的研究——Ⅴ.Cp_2MH_2(M=Zr,Hf)与RNCS(R=n-Bu,c-C_6H_(11),C_6H_5,2-C_(10)H_7)、CS_2的反应

本文研究了Cp_2ZrH_2与CS_2、RNCS(R=n-Bu,c-C_6H_11,C_6H_5,2-C_(10)H_7)和Cp_2HfH_2与c-C_6H_(11)NCS的反应,探讨了在这类新型脱硫反应中锆氢与铪氢配合物化学反应性能上的差异.从以上反应中分别得到两个硫桥同核双金属配合物(Cp_2MS)_2(1,M=Zr;2,M=Hf)和有机铪配合物Cp_2Hf[SC(H)NR]_2(3,R=c-C_6H_(11)).产物结构由元素分析、IR、~1H和~(13)C NMR及MS谱分析鉴定,产物1的晶体结构由X光四圆衍射方法测定,有机产物X=CH_2和CH_3X(H)(X=S,NR)由GC-MS谱分析测定.     

Halide coordination of perhalocyclohexasilane Si6X12 (X=Cl or Br)

The addition of halide anions (X' = Cl(-), Br(-), or I(-)) to perhalocyclohexasilane Si(6)X(12) (X = Cl or Br) led to the formation of complexes comprising [Si(6)X(12)X'(2)](2-) dianions. An upfield shift in the (29)Si NMR spectra was noted upon coordination, and structural determination by X-ray crystallography showed that the dianions adopt an "inverse sandwich" structure where the six cyclic silicon atoms form a planar hexagon with the two halide anions X' located on the 6-fold axis equally disposed above and below the plane of the Si(6) ring. Additionally, these apical X' atoms are within the van der Waals bonding distance to the silicon ring atoms, indicating a strong interaction between X' and silicon atoms. These results detail crystallographic variations within the halogen series providing further insight into the nature of the Lewis acid sites above and below the Si(6)X(12) ring, where interactions with hard Lewis bases such as halide anions are observed. Interestingly, the stereochemistry of the silicon atoms in [Si(6)X(12)X'(2)](2-) is not affected much by the size or electronegativity of the halogen atoms.     

Ruthenium complexes with tridentate PNX (X = O, S) donor ligands

The ligands, PhPNXMe (1), PhPNXPh (2), and PhPNSMe (3), (PhPNX = 2-Ph2P-C6H4CH[double bond, length as m-dash]NC6H4X-2; X = O, S) have been prepared. A range of new ruthenium complexes were synthesised using these and related ligands, namely: [{RuCl(PhPNO)}2Cl] (4), [Ru(PhPNO)2] (5), [RuCl(PhPNXR)(PPh3)]BPh4 [X = O, R = Me (6); X = O, R = Ph (7); X = S, R = Me (8)], [{RuCl(PhPNX'R)}2Cl]X [X' = O, R = Me, X = Cl(-) (9); X' = S, R = Me, X = BPh4(-) or PF6(-) (10)], and [RuCl(PhPNO-eta 6C6H5)]BPh4 (11). The catalytic activity of these complexes with respect to the hydrosilyation of acetophenone and the hydrogenation of styrene has been investigated, giving an insight into the requirements for an active complex in these reactions.     

Alkinylverbindungen von übergangsmetallen : XXXIX. Planare palladium(II) komplexe des typs trans-[p-C6H4(CCPd(X)(PEt3)2)2](n+2)+ (n = summe der ionenladungen von X)

Preparation and properties of the diamagnetic planar complexes trans-[p-C₆H₄(CCPd(X)(PEt₃)₂)₂] (X = Cl, Br, I, NCS) and trans-[p-C₆H₄(CCPd(X)(PEt₃)₂)₂](ClO₄)₂ (X = PEt₃, pyridine) are described. The structures of the compounds have been determined by ³¹P and ¹H NMR spectroscopy. The IR spectra are discussed.     

Synthesis and ligand-based mixed valency of cis- and trans-Cr(III)(X(4)SQ)(X(4)Cat)(L)(n) (X = Cl and Br,n = 1 or 2) complexes: effects of solvent media on intramolecular charge distribution and ligand dissociation of Cr(III)(X(4)SQ)(3)

The treatment of Cr(III)(X(4)SQ)(3) (SQ = o-semiquinonate; X = Cl and Br) with acetonitrile affords trans-Cr(III)(X(4)SQ)(X(4)Cat)(CH(3)CN)(2) (X = Cl (1) and Br (2)). In the presence of 2,2'-bipyridine (bpy) or 3,4,7,8-tetramethyl-1,10-phenanthrene (tmphen), the reaction affords Cr(III)(X(4)SQ)(X(4)Cat)(bpy).nCH(3)CN (X = Cl, n = 1 (3); X = Br, n = 0.5 (4)) or Cr(III)(X(4)SQ)(X(4)Cat)(tmphen) (X = Cl (5) and Br (6)), respectively. All of the complexes show a ligand-based mixed-valence (LBMV) state with SQ and Cat ligands. The LBMV state was confirmed by the presence of the interligand intervalence charge-transfer band. Spectroscopic studies in several solvent media demonstrate that the ligand dissociation included in the conversion of Cr(III)(X(4)SQ)(3) to 1-6 occurs only in solvents with relatively high polarity. On the basis of these results, the effects of solvent media were examined and an equilibrium, Cr(III)(X(4)SQ)(3) <--> Cr(III)(X(4)BQ)(X(4)SQ)(X(4)Cat) (BQ = o-benzoquinone), is proposed by assuming an interligand electron transfer induced by solvent polarity.     

DFT study on the reed diethylaluminum cation-like system: structure and bonding in Et(2)Al(CB(11)H(6)X(6)) (X = Cl, Br)

Electronic and molecular structure has been investigated in the diethylaluminum cation-like system Et(2)Al(CB(11)H(6)X(6)) (1, X = Cl; 2, X = Br) and neutral compounds AlX(3) (X = Cl, Br, Me, C(6)H(5)) with DFT B3LYP and BP86 levels of theory. The calculated geometries of Et(2)Al(CB(11)H(6)X(6)) (1, X = Cl; 2, X = Br) are in excellent agreement with those determined experimentally by X-ray crystallography. The Al-X bond distances 2.442, 2.445 A in 1 and 2.579, 2.589 A in 2 are longer than those expected for single bonds based on covalent radius predictions (Al-Cl = 2.15 A and Al-Br = 2.32 A) and those observed for bridged Al-X-Al bonds (2.21 A in Al(2)Cl(6), 2.33 A in Al(2)Br(6)) and are close to sum of ionic radii of Al(3+) and X(-) (Al-Cl = 2.35 A and Al-Br = 2.50 A). The optimized geometries of the neutral compounds AlX(3) (X = Cl, Br, Me(3), C(6)H(5)) at BP86/TZ2P show Al-Cl = 2.088 A in AlCl(3), Al-Br = 2.234 A in AlBr(3), Al-C = 1.973 A in AlMe(3), Al-C = 2.255 A in Al(C(6)F(5))(3). These bond distances are similar to those expected for single bonds based on covalent radius predictions. The calculated charge distribution indicates that the aluminum atom carries a significant positive charge while the ethyl and carborane groups are negatively charged. The Cl and Br atoms in compounds 1 and 2 are slightly positive while, in neutral compounds AlX(3) (X = Cl, Br, Me(3), C(6)H(5)), X is negatively charged. Energy decomposition analysis of Et(2)Al(delta)(+)(carborane)(delta)(-) shows that the bonding between the fragments is more than half electrostatic. The ionic character of the Al...Cl bonds in compound 1(59.8%) is greater than the Al.Br bonds in the compound 2 (57.9%). This quantifies and gives legitimacy to the designation of these types of compounds as "ion-like". The Al-X bonding in AlX(3) is mainly covalent with percentage ionic character 28.2% in AlCl(3), 31.5% in AlBr(3), 25.6% in AlMe(3), 18.4% in Al(C(6)F(5))(3).     

Synthesis and studies of CuHg(NCX)4 (X = S,Se) and their complexes and application of the softness parameter in the elucidation of their structure

Complexes of CuHg(NCS)₄, CuHg(NCS)₂ (NCSe)₂ and CuHg(NCSe)₄ with tetrahydrofuran, dioxane, pyridine, 2-aminopyridine, nicotinamide, bipyridine and phenanthroline have been prepared and comparative studies made. Bipyridine and phenanthroline form cationic—anionic [CuL₃]²⁺ [Hg(SCN)₄]^2? (L = bipy, phen) complexes with CuHg(NCS)₄ and dinuclear bridged complexes with CuHg(NCSe)₄ and CuHg(NCS)₂ (NCSe)₂. For other ligands the nature of the complexes is binuclear or polynuclear. The comparative stability of the -XCN- bridge (X = S, Se) is CuHg(NCSe)₄ > CuHg(NCS)₂ (NCSe)₂ > CuHg(NCS)₄.     

Microhydration of X2 gas (X = Cl, Br, and I): a theoretical study on X2.nH2O clusters (n = 1-8)

Structure and properties of hydrated clusters of halogen gas, X2.nH2O (X = Cl, Br, and I; n = 1-8) are presented following first principle based electronic structure theory, namely, BHHLYP density functional and second-order Moller-Plesset perturbation (MP2) methods. Several geometrical arrangements are considered as initial guess structures to look for the minimum energy equilibrium structures by applying the 6-311++G(d,p) set of the basis function. Results on X2-water clusters (X = Br and I) suggest that X2 exists as a charge separated ion pair, X+delta-X-delta in the hydrated clusters, X2.nH2O (n > or = 2). Though the optimized structures of Cl2.nH2O clusters look like X2.nH2O (X = Br and I) clusters, Cl2 does not exist as a charge separated ion pair in the presence of solvent water molecules. The calculated interaction energy between X2 and solvent water cluster increases from Cl2.nH2O to I2.nH2O clusters, suggesting solubility of gas-phase I2 in water to be a maximum among these three systems. Static and dynamic polarizabilities of hydrated X2 clusters, X2.nH2O, are calculated and observed to vary linearly with the size (n) of these water clusters with correlation coefficient >0.999. This suggests that the polarizability of the larger size hydrated clusters can be reliably predicted. Static and dynamic polarizabilities of these hydrated clusters grow exponentially with the frequency of an external applied field for a particular size (n) of hydrated cluster.     

Co-ordination compounds of diacetyldihydrazone and diacetylbis(monomethylhydrazone)

Summary Diacetyldihydrazone (DADH) forms only six-coordinate complexes with iron(II), cobalt(II), nickel(II) and zinc(II). In M(DADH)₂X₂ (M=Fe, X=Br or I; M=Co, X=I; M=Ni, X=Cl, Br or NCS) the ligand is chelating in the [M(DADH)₃]²⁺ cations, while in M(DADH)₂X₂ (M=Co, X=Cl or Br; M=Ni, X=Cl or Br) the ligand is probably bridging and bidentate. Diacetylbismonomethylhydrazone (DAMH), by contrast, forms predominantly tetrahedral complexes M(DAMH)X₂ (M=Fe or Co, X=Cl or Br; M=Ni, X=Br; M=Co, X=NCS; M=Zn, X=Cl, Br or NCS) and some octahedral complexes M(DAMH)₂X₂ (M=Co, X=NCS; M=Ni, X=Br). The i.r. spectra, electronic spectra and magnetic moments of the complexes are discussed.     

Redox energetics of hypercloso boron hydrides B(n)H(n) (n = 6-13) and B12X12 (X = F, Cl, OH, and CH3)

The reduction potentials (E°(Red) versus SHE) of hypercloso boron hydrides B(n)H(n) (n = 6-13) and B(12)X(12) (X = F, Cl, OH, and CH(3)) in water have been computed using the Conductor-like Polarizable Continuum Model (CPCM) and the Solvation Model Density (SMD) method for solvation modeling. The B3LYP/aug-cc-pvtz and M06-2X/aug-cc-pvtz as well as G4 level of theory were applied to determine the free energies of the first and second electron attachment (ΔG(E.A.)) to boron clusters. The solvation free energies (ΔG(solv)) greatly depend on the choice of the cavity set (UAKS, Pauling, or SMD) while the dependence on the choice of exchange/correlation functional is modest. The SMD cavity set gives the largest ΔΔG(solv) for B(n)H(n)(0/-) and B(n)H(n)(-/2-) while the UAKS cavity set gives the smallest ΔΔG(solv) value. The E°(Red) of B(n)H(n)(-/2-) (n = 6-12) with the G4/M06-2X(Pauling) (energy/solvation(cavity)) combination agrees within 0.2 V of experimental values. The experimental oxidative stability (E(1/2)) of B(n)X(n)(2-) (X = F, Cl, OH, and CH(3)) is usually located between the values predicted using the B3LYP and M06-2X functionals. The disproportionation free energies (ΔG(dpro)) of 2B(n)H(n)(-) → B(n)H(n) + B(n)H(n)(2-) reveal that the stabilities of B(n)H(n)(-) (n = 6-13) to disproportionation decrease in the order B(8)H(8)(-) > B(9)H(9)(-) > B(11)H(11)(-) > B(10)H(10)(-). The spin densities in B(12)X(12)(-) (X = F, Cl, OH, and CH(3)) tend to delocalize on the boron atoms rather than on the exterior functional groups. The partitioning of ΔG(solv)(B(n)H(n)(2-)) over spheres allows a rationalization of the nonlinear correlation between ΔG(E.A.) and E°(Red) for B(6)H(6)(-/2-), B(11)H(11)(-/2-), and B(13)H(13)(-/2-).     

Soluble mu-Fi bridged niobium clusters: synthesis and crystal structures of (Et4N)6[Nb6Fi6Bri6(NCS)a6]Br2 and Cs1.6K2.4[Nb6Fi6Ii6(NCS)a6

Two new anions [Nb(6)F(i)(6)X(i)(6)(NCS)(a)(6)](4-)(X = Br, I) based on octahedral niobium clusters with edge-bridging F ligands have been prepared by reaction of Cs(3)Nb(6)F(6)Br(12) and Cs(4)Nb(6)F(8.5)I(9.5) with aqueous solution of KSCN. The anions were isolated as (Et(4)N)(6)[Nb(6)F(6)Br(6)(NCS)(6)]Br(2) (1)and Cs(1.6)K(2.4)[Nb(6)F(6)I(6)(NCS)(6)] (2) salts.     

Cationic P-S-X cages (X=Br, I)

The first condensed-phase preparation of ternary P-Ch-X cations (Ch=O-Te, X=F-I) is reported: [P5S3X2]+, [P5S2X2]+, and [P4S4X]+ (X=Br, I). [P5S3X2]+ is formed from the reaction of the Ag+/PX3 reagent with P4S3. The [P5S3X2]+ ions have a structure that is related to P4S5 by replacing P=S by P+--X and S in the four-membered ring by P(X). We provide evidence that the active ingredient of the Ag+/PX3 reagent is the (H2CCl2)Ag-X-PX2+ cation. The latter likely reacts with the HOMO of P4S3 in a concerted HOMO-LUMO addition to give the P5S3X2+ ion as the first species visible in situ in the low-temperature 31P NMR spectrum. The [P5S3X2]+ ions are metastable at -78 degrees C and disproportionate at slightly higher temperatures to give [P5S2X2]+ and [P4S4X]+, probably with the extrusion of 1/n (PX)n (X=Br, I). All six new cage compounds have been characterized by multinuclear NMR spectroscopy and, in part, by IR or Raman spectroscopy. The [P5S2X2]+ salts have a nortricyclane skeleton and were also characterized by X-ray crystallography. The structure of the [P4S4X]+ ion is related to that of P4S5 in that the exo-cage P=S bond is replaced by an isoelectronic P+--X moiety.