Synthesis and structural characterization of a new series of vanadoselenites, [Se(x)V(4-x)O(12-x)](4-x)- (x=1,2)

Two new vanadoselenites, [SeV(3)O(11)](3)(-) and [Se(2)V(2)O(10)](2)(-), were synthesized by reacting SeO(2) with VO(3)(-). Single-crystal X-ray structural analyses of [(n-C(4)H(9))(4)N](3)[SeV(3)O(11)].0.5H(2)O [orthorhombic, space group P2(1)2(1)2, a = 22.328(5) A, b = 44.099(9) A, c = 12.287(3) A, Z = 8] and [[(C(6)H(5))(3)P](2)N](2)[Se(2)V(2)O(10)] [monoclinic, space group P2(1)/n, a = 12.2931(3) A, b = 13.5101(3) A, c = 20.9793(5) A, beta = 106.307(1) degrees, Z = 2] revealed that both anions are composed of Se(x)()V(4)(-)(x)()O(4) rings. The (51)V, (77)Se, and (17)O NMR spectra established that both [SeV(3)O(11)](3)(-) and [Se(2)V(2)O(10)](2)(-) anions maintain this ring structure in solution.     

Reactions of [Ru(H(2)O)(6)](2+) with water-soluble tertiary phosphines

In aqueous solutions under mild conditions, [Ru(H(2)O)(6)](2+) was reacted with various water-soluble tertiary phosphines. As determined by multinuclear NMR spectroscopy, reactions with the sulfonated arylphosphines L =mtppms, ptppms and mtppts yielded only the mono- and bisphosphine complexes, [Ru(H(2)O)(5)L](2+), cis-[Ru(H(2)O)(4)L(2)](2+), and trans-[Ru(H(2)O)(4)L(2)](2+) even in a high ligand excess. With the small aliphatic phosphine L = 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1(3,7)]decane (pta) at [L]:[Ru]= 12:1, the tris- and tetrakisphosphino species, [Ru(H(2)O)(3)(pta)(3)](2+), [Ru(H(2)O)(2)(pta)(4)](2+), [Ru(H(2)O)(OH)(pta)(4)](+), and [Ru(OH)(2)(pta)(4)] were also detected, albeit in minor quantities. These results have significance for the in situ preparation of Ru(II)-tertiary phosphine catalysts. The structures of the complexes trans-[Ru(H(2)O)(4)(ptaMe)(2)](tos)(4)x2H(2)O, trans-[Ru(H(2)O)(4)(ptaH)(2)](tos)(4)[middle dot]2H(2)O, and trans-mer-[RuI(2)(H(2)O)(ptaMe)(3)]I(3)x2H(2)O, containing protonated or methylated pta ligands (ptaH and ptaMe, respectively) were determined by single crystal X-ray diffraction.     

Preparation and characterization of the argentates: [Ag[P(CF(3))(2)](2)](-), [Ag[(micro-P(CF(3))(2))M(CO)(5)](2)](-) (M = Cr, W), and [Ag[(micro-P(C(6)F(5))(2))W(CO)(5)](2)](-): X-ray crystal structure of [K(18-crown-6)][Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)

The first example of a mononuclear diphosphanidoargentate, bis[bis(trifluoromethyl)phosphanido]argentate, [Ag[P(CF(3))(2)](2)](-), is obtained via the reaction of HP(CF(3))(2) with [Ag(CN)(2)](-) and isolated as its [K(18-crown-6)] salt. When the cyclic phosphane (PCF(3))(4) is reacted with a slight excess of [K(18-crown-6)][Ag[P(CF(3))(2)](2)], selective insertion of one PCF(3) unit into each silver phosphorus bond is observed, which on the basis of NMR spectroscopic evidence suggests the [Ag[P(CF(3))P(CF(3))(2)](2)](-) ion. On treatment of the phosphane complexes [M(CO)(5)PH(CF(3))(2)] (M = Cr, W) with [K(18-crown-6)][Ag(CN)(2)], the analogous trinuclear argentates, [Ag[(micro-P(CF(3))(2))M(CO)(5)](2)](-), are formed. The chromium compound [K(18-crown-6)][Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)] crystallizes in a noncentrosymmetric space group Fdd2 (No. 43), a = 2970.2(6) pm, b = 1584.5(3) pm, c = 1787.0(4), V = 8.410(3) nm(3), Z = 8. The C(2) symmetric anion, [Ag[(micro-P(CF(3))(2))Cr(CO)(5)](2)](-), shows a nearly linear arrangement of the P-Ag-P unit. Although the bis(pentafluorophenyl)phosphanido compound [Ag[P(C(6)F(5))(2)](2)](-) has not been obtained so far, the synthesis of its trinuclear counterpart, [K(18-crown-6)][Ag[(micro-P(C(6)F(5))(2))W(CO)(5)](2)], was successful.     

(Ph)3PBr][Br7], [(Bz)(Ph)3P]2[Br8], [(n-Bu)3MeN]2[Br20], [C4MPyr]2[Br20], and [(Ph)3PCl]2[Cl2I14]: extending the horizon of polyhalides via synthesis in ionic liquids

The five polyhalides [(Ph)(3)PBr][Br(7)], [(Bz)(Ph)(3)P](2)[Br(8)], [(n-Bu)(3)MeN](2)[Br(20)], [C(4)MPyr](2)[Br(20)] ([C(4)MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)(3)PCl](2)[Cl(2)I(14)] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)(3)PBr][Br(7)] and [(Bz)(Ph)(3)P](2)[Br(8)] contain discrete pyramidal [Br(7)](-) and Z-shaped [Br(8)](2-) polybromide anions. [(n-Bu)(3)MeN](2)[Br(20)] and [C(4)MPyr](2)[Br(20)] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)(3)PCl](2)[Cl(2)I(14)] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br(2) and ICl and that, on the other hand, reduces the high volatility of the molecular halogens.     

Novel aggregation of [Ni(thiolato)2(amine)2]-type square planes assisted by silver(I) ions

Treatment of [Ni(L)][L =((-)SCH(2)CH(2)NH[double bond, length as m-dash]C(CH(3))-)(2)] with Ag(+) in water gave a pinwheel-like S-bridged Ni(II)(3)Ag(I)(2) structure in [Ag(2)[Ni(L)](3)](2+), which further reacted with [Ni(L)] to produce a Ni(II)(4)Ag(I)(2) structure in [Ag(2)[Ni(L)](4)](2+) and a Ni(II)(7)Ag(I)(4) structure in [Ag(4)[Ni(L)](7)](4+).     

Metallosupramolecular chemistry with bis(benzene-o-dithiolato) ligands

The bis(benzene-o-dithiol) ligands H(4)-1, H(4)-2, and H(4)-3 react with [Ti(OC(2)H(5))(4)] to give dinuclear triple-stranded helicates [Ti(2)L(3)](4)(-) (L = 1(4)(-), 2(4)(-), 3(4)(-)). NMR spectroscopic investigations revealed that the complex anions possess C(3) symmetry in solution. A crystal structure analysis for (PNP)(4)[Ti(2)(2)(3)] ((PNP)(4)[14]) confirmed the C(3) symmetry for the complex anion in the solid state. The complex anion in Li(PNP)(3)[Ti(2)(1)(3)] (Li(PNP)(3)[13]) does not exhibit C(3) symmetry in the solid state due to the formation of polymeric chains of lithium bridged complex anions. Complexes [13](4)(-) and [14](4)(-) were obtained as racemic mixtures of the Delta,Delta and Lambda,Lambda isomers. In contrast to that, complex (PNP)(4)[Ti(2)(3)(3)] ((PNP)(4)[15]) with the enantiomerically pure chiral ligand 3(4)(-) shows a strong Cotton effect in the CD spectrum, indicating that the chirality of the ligands leads to the formation of chiral metal centers. The o-phenylene diamine bridged bis(benzene-o-dithiol) ligand H(4)-4 reacts with Ti(4+) to give the dinuclear double-stranded complex Li(2)[Ti(2)(4)(2)(mu-OCH(3))(2)] containing two bridging methoxy ligands between the metal centers. The crystal structure analysis and the (1)H NMR spectrum of (Ph(4)As)(2)[Ti(2)(4)(2)(mu-OCH(3))(2)] ((Ph(4)As)(2)[(16]) reveal C(2) symmetry for the anion [Ti(2)(4)(2)(mu-OCH(3))(2)](2)(-). For a comparative study the dicatechol ligand H(4)-5, containing the same o-phenylene diamine bridging group as the bis(benzene-o-dithiol) ligands H(4)-4, was prepared and reacted with [TiO(acac)(2)] to give the dinuclear complex anion [Ti(2)(5)(2)(mu-OCH(3))(2)](2)(-). The molecular structure of (PNP)(2)[Ti(2)(5)(2)(mu-OCH(3))(2)] ((PNP)(2)[17]) contains a complex anion which is similar to [16](2)(-), with the exception that strong N-H...O hydrogen bonds are formed in complex anion [17](2)(-), while N-H...S hydrogen bonds are absent in complex anion [16](2)(-).     

A variable Ag-Cr-Oxalate channel lattice: [M(x)Ag(0.5)(-)(x)(H(2)O)(3)]@[Ag(2.5)Cr(C(2)O(4))(3)], M = K, Cs, Ag

Reaction of aqueous AgNO(3) with aqueous M(3)[Cr(ox)(3)] in >or=3:1 molar ratio causes the rapid growth of large, cherry-black, light-stable crystals which are not Ag(3)[Cr(ox)(3)], but [M(0.5)(H(2)O)(3)]@[Ag(2.5)Cr(ox)(3)] (ox(2)(-) = oxalate, C(2)O(4)(2)(-); M = Na, K, Cs, Ag, or mixtures of Ag and a group 1 element). The structure of these crystals contains an invariant channeled framework, with composition [[Ag(2.5)Cr(ox)(3)](-)(0.5)]( infinity ), constructed with [Cr(ox)(3)] coordination units linked by Ag atoms through centrosymmetric [Cr-O(2)C(2)O(2)-Ag](2) double bridges. The framework composition [Ag(2.5)Cr(ox)(3)](-)(0.5) occurs because one Ag is located on a 2-fold axis. Within the channels there is a well-defined and ordered set of six water molecules, strongly hydrogen bonded to each other and some of the oxalate O atoms. This invariant channel plus water structure accommodates group 1 cations, and/or Ag cations, in different locations and in variable proportions, but always coordinated by channel water and some oxalate O atoms. The general formulation of these crystals is therefore [M(x)Ag(0.5-x)(H(2)O)(3)]@[Ag(2.5)Cr(ox)(3)]. Five different crystals with this structure are reported, with compositions 1 Ag(0.5)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 2 Cs(0.19)Ag(0.31)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 3 K(0.28)Ag(0.22)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), 4 Cs(0.41)Ag(0.09)[Ag(2.5)Cr(ox)(3)](H(2)O)(3), and 5 Cs(0.43)Ag(0.07) [Ag(2.5)Cr(ox)(3)](H(2)O)(3). All crystallize in space group C2/c, with a approximately 18.4, b approximately 14.6, c approximately 12.3 A, beta approximately 113 degrees. Pure Ag(3)[Cr(ox)(3)](H(2)O)(3), which has the same crystal structure (1), was obtained from water by treating Li(3)[Cr(ox)(3)] with excess AgNO(3). Complete dehydration of all of these compounds occurs between 30 and 100 degrees C, with loss of diffraction, but rehydration by exposure to H(2)O(g) at ambient temperature leads to recovery of the original diffraction pattern. In single crystals, this reversible dehydration-hydration occurs without visually evident crystal change, but with loss of mechanical strength. We postulate a general mechanism for transport of water molecules along the channels, associated with local partial collapses of the channel framework, with concomitant bending but little breaking of the host Ag-O and Cr-O bonds, which is readily reversed.     

Two enantiomers of [Cu(3)(mnt)(3)](3-) as ligands to Cu(i) or Ag(i) in building [Cu(6)M(2)(mnt)(6)](4-) complexes (M = Cu or Ag) with the reversal of the reaction by X(-) (X = Cl, Br)

Two enantiomers of [Bu(4)N](3)[Cu(3)(mnt)(3)] () formed by Na(2)(mnt) (mnt = maleonitriledithiolate, [S(2)C(2)(CN)(2)](2-)) and CuCl in a 1 : 1 molar ratio react further with MCl (M = Cu or Ag) involving both the enantiomers of to produce the larger complex, [Bu(4)N](4)[Cu(6)M(2)(mnt)(6)] (M = Cu (2), Ag (3)) from which the capped Cu(+) or Ag(+) ion can readily be removed by Bu(4)NX (X = Cl, Br), reverting or back to . Such reversal does not work with non-coordinating anions like BF(4)(-), ClO(4)(-) and PF(6)(-).     

Bi-, tetra-, and hexanuclear AuI and binuclear AgI complexes and AgI coordination polymers containing phenylaminobis(phosphonite), PhN{P(OC6H4OMe-o)2}2, and pyridyl ligands

The reactions of phenylaminobis(phosphonite), PhN{P(OC6H4OMe-o)2}2 (1) (PNP), with [AuCl(SMe2)] in appropriate ratios, afford the bi- and mononuclear complexes, [(AuCl)2(micro-PNP)] (2) and [(AuCl)(PNP)]2 (3) in good yield. Treatment of 2 with 2 equiv of AgX (X = OTf or ClO4) followed by the addition of 1 or 2,2'-bipyridine affords [Au2(micro-PNP)2](OTf)2 (4) and [Au2(C10H8N2)2(micro-PNP)](ClO4)2 (5), respectively. Similarly, the macrocycles [Au4(C4H4N2)2(micro-PNP)2](ClO4)4 (6), [Au4(C10H8N2)2(micro-PNP)2](ClO4)4 (7), and [Au6(C3H3N3)2(micro-PNP)3](ClO4)6 (8) are obtained by treating 2 with pyrazine, 4,4'-bipyridine, or 1,3,5-triazine in the presence of AgClO 4. The reaction of 1 with AgOTf in a 1:2 molar ratio produces [Ag2(micro-OTf)2(micro-PNP)] (9). The displacement of triflate ions in 9 by 1 leads to a disubstituted derivative, [Ag2(micro-PNP)3](OTf)2 (10). The equimolar reaction of 1 with AgClO4 in THF affords [Ag2(C4H8O)2(micro-PNP)2](ClO4)2 (11). Treatment of 1 with AgClO4 followed by the addition of 2,2'-bipyridine affords a discrete binuclear complex, [Ag2(C10H8N2)2(micro-PNP)](ClO4)2 (12), whereas similar reactions with 4,4'-bipyridine or pyrazine produce one-dimensional zigzag Ag (I) coordination polymers, [Ag2(C10H8N2)(micro-ClO4)(ClO4)(micro-PNP)]n (13) and [Ag2(C4H4N2)(micro-ClO4)(ClO4)(micro-PNP)]n (14) in good yield. The nature of metal-metal interactions in compounds 2, 4, 5, and 12 was analyzed theoretically by performing HF and CC calculations. The structures of the complexes 2, 4, 5, 7, 9, 12, and 14 are confirmed by single crystal X-ray diffraction studies.     

Synthesis, Characterization, and Comparative Properties of [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] and [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)

The reaction of [PPN](2)[Re(6)C(CO)(19)] with Mo(CO)(6) and Ru(3)(CO)(12) under sunlamp irradiation provided the new mixed-metal clusters [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] and [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)], which were isolated in yields of 85% and 61%, respectively. The compound [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] crystallizes in the monoclinic space group P2(1)/c with a = 20.190 (7) ?, b = 16.489 (7) ?, c = 27.778 (7) ?, beta = 101.48 (2) degrees, and Z = 4 (at T = -75 degrees C). The cluster anion is composed of a Re(6)C octahedral core with a face capped by a Mo(CO)(4) fragment. There are three terminal carbonyl ligands coordinated to each rhenium atom. The four carbonyl ligands on the molybdenum center are essentially terminal, with one pair of carbonyl ligands (C72-O72 and C74-O74) subtending a relatively large angle at molybdenum (C72-Mo-C74 = 147.2(9) degrees ), whereas the remaining pair of carbonyl ligands (C71-O71 and C73-O73) subtend a much smaller angle (C71-Mo-C73 = 100.5(9) degrees ). The (13)C NMR spectrum of (13)CO-enriched [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] shows signals for four sets of carbonyl ligands at -40 degrees C, consistent with the solid state structure, but the carbonyl ligands undergo complete scrambling at ambient temperature. The (13)C NMR spectrum of (13)CO-enriched [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)] at 20 degrees C is consistent with the expected structure of an octahedral Re(6)C(CO)(18) core capped by a Ru(CO)(3) fragment. The visible spectrum of [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)] shows a broad, strong band at 670 nm (epsilon = 8100), whereas all of the absorptions of [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)] are at higher energy. An irreversible oxidation wave with E(p) at 0.34 V is observed for [PPN](2)[Re(6)C(CO)(18)Mo(CO)(4)], whereas two quasi-reversible oxidation waves with E(1/2) values of 0.21 and 0.61 V (vs Ag/AgCl) are observed for [PPN](2)[Re(6)C(CO)(18)Ru(CO)(3)]. The molybdenum cap in [Re(6)C(CO)(18)Mo(CO(4))](2-) is cleaved by heating in donor solvents, and by treatment with H(2), to give largely [H(2)Re(6)C(CO)(18)](2-). In contrast, [Re(6)C(CO)(18)Ru(CO)(3)](2-) shows no tendency to react under similar conditions.     

Structural and dynamical aspects of alkylammonium salts of a silicodecatungstate as heterogeneous epoxidation catalysts

The structural and dynamical aspects of alkylammonium salts of a silicodecatungstate [(CH(3))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C1], [(n-C(3)H(7))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C3], [(n-C(4)H(9))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C4], and [(n-C(5)H(11))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C5] were investigated. The results of sorption isotherms, XRD analyses, and solid-state NMR spectroscopy show that facile sorption of solvent molecules, flexibility of structures, and high mobility of alkylammonium cations are crucial to the uniform distribution of reactant and oxidant molecules throughout the bulk solid, which are related to the high catalytic activities for epoxidation of alkenes.     

A copper(I) homocubane collapses to a tetracapped tetrahedron upon hydride insertion

The hydrido copper(I) and silver(I) clusters incorporating 1,1-dicyanoethylene-2,2-dithiolate (i-MNT) ligands are presented in this paper. Reactions of M(I) (M = Cu, Ag) salts, [Bu(4)N](2)[S(2)CC(CN)(2)], with the anion sources ([Bu(4)N][BH(4)] for H(-), [Bu(4)N][BD(4)] for D(-)) in an 8:6:1 molar ratio in THF produce octanuclear penta-anionic Cu(I)/Ag(I) clusters, [Bu(4)N](5)[M(8)(X){S(2)CC(CN)(2)}(6)] (M = Cu, X = H, 1(H); X = D, 1(D); M = Ag, X = H, 2(H); X = D, 2(D)). They can also be produced from the stoichiometric reaction of M(8)(i-MNT)(6)(4-) with the ammonium borohydride. All four compounds have been fully characterized spectroscopically ((1)H and (13)C NMR, IR, UV-vis) and by elemental analyses. The deuteride-encapsulated Cu(8)/Ag(8) clusters of 1(D) and 2(D) are also characterized by (2)H NMR. X-ray crystal structures of 1(H) and 2(H) reveal a hydride-centered tetracapped tetrahedral Cu(8)/Ag(8) core, which is inscribed within an S(12) icosahedron formed by six i-MNT ligands, each in a tetrametallic-tetraconnective (μ(2), μ(2)) bonding mode. The encapsulated hydride in 2(H) is unequivocally characterized by both (1)H and (109)Ag NMR spectroscopies, and the results strongly suggest that the hydride is coupled to eight magnetically equivalent silver nuclei on the NMR time scale. Therefore, a fast interchange between the vertex and capping silver atoms in solution gives a plausible explanation for the perceived structural differences between the Ag(8) geometry deduced from the X-ray structure and the NMR spectra.     

Synthesis, crystal structure and optical properties of [Ag(UO2)3(OAc)9][Zn(H2O)4(CH3CH2OH)2]: a novel compound containing closed-shell 3d10, 4d10 and 5d10 metal ions

[Ag(UO(2))(3) (OAc)(9)][Zn(H(2)O)(4)(CH(3)CH(2)OH)(2)] (, OAc = CH(3)COO(-)) crystallized from an ethanol solution and its structure was determined by IR spectroscopy, elemental analysis, (1)H NMR, (13)C NMR and X-ray crystallography; it is composed of [Zn(H(2)O)(4)(CH(3)CH(2)OH)(2)](2+) cations and [Ag(UO(2))(3)(OAc)(9)](2-) anions in which triuranyl [(UO(2))(OAc)(3)](3) clusters are linked by the Ag ion.     

Gold(I) complexes bearing mixed-donor ligands derived from N-heterocyclic carbenes

The new 2-phenylthiocarbamoyl-1,3-dimesitylimidazolium inner salt (IMes·CSNPh) reacts with [AuCl(L)] in the presence of NH(4)PF(6) to yield [(L)Au(SCNPh·IMes)](+) (L = PMe(3), PPh(3), PCy(3), CNBu(t)). The carbene-containing precursor [(IDip)AuCl] reacts with IMes·CSNPh under the same conditions to afford the complex [(IDip)Au(SCNPh·IMes)](+) (IDip = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). Treatment of the diphosphine complex [(dppm)(AuCl)(2)] with one equivalent of IMes·CSNPh yields the digold metallacycle, [(dppm)Au(2)(SCNPh·IMes)](2+), while reaction of [L(2)(AuCl)(2)] with two equivalents of IMes·CSNPh results in [(L(2)){Au(SCNPh·IMes)}(2)](2+) (L(2) = dppb, dppf, or dppa; dppb = 1,4-bis(diphenylphosphino)butane, dppf = 1,1'-bis(diphenylphosphino)ferrocene, dppa = 1,4-bis(diphenylphosphino)acetylene). The homoleptic complex [Au(SCNPh·IMes)(2)](+) is formed on reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with two equivalents of the imidazolium-2-phenylthiocarbamoyl ligand. This product reacts with AgOTf to yield the mixed metal compound [AuAg(SCNPh·IMes)(2)](2+). Over time, the unusual trimetallic complex [Au(AgOTf)(2)(SCNPh·IMes)(2)](+) is formed. The sulfur-oxygen mixed-donor ligands IMes·COS and SIMes·COS (SIMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) were used to prepare [(L)Au(SOC·IMes)](+) and [(L)Au(SOC·SIMes)](+) from [(L)AuCl] (L = PPh(3), CN(t)Bu). The bimetallic examples [(dppf){Au(SOC·IMes)}(2)](2+) and [(dppf){Au(SOC·SIMes)}(2)](2+) were synthesized from the reaction of [(dppf)(AuCl)(2)] with the appropriate ligand. Reaction of [(tht)AuCl] with one equivalent of IMes·COS or SIMes·COS yields [Au(SOC·IMes)(2)](+) and [Au(SOC·SIMes)(2)](+), respectively. The compounds [(Ph(3)P)Au(SCNPh·IMes)]PF(6), [(Cy(3)P)Au(SCNPh·IMes)]PF(6) and [Au(AgOTf)(2)(SCNPh·IMes)(2)]OTf were characterized crystallographically.     

Synthesis and characterization of the silver maleonitrilediselenolates and silver maleonitriledithiolates [K([2.2.2]-cryptand)]4[Ag4(Se2C2(CN)2)4], [Na([2.2.2]-cryptand)]4[Ag4(S2C2(CN)2)4].0.33MeCN, [NBu4]4[Ag4(S2C2(CN)2)4], [K([2.2.2]-cryptand)]3[Ag(Se2C2(CN)2)2].2MeCN, and [Na([2.2.2]-cryptand)]3[Ag(S2C2(CN)2)2

Reaction of AgBF(4), KNH(2), K(2)Se, Se, and [2.2.2]-cryptand in acetonitrile yields [K([2.2.2]-cryptand)](4)[Ag(4)(Se(2)C(2)(CN)(2))(4)] (1). In the unit cell of 1 there are four [K([2.2.2]-cryptand)](+) units and a tetrahedral Ag(4) anionic core coordinated in mu(1)-Se, mu(2)-Se fashion by each of four mns ligands (mns = maleonitrilediselenolate, [Se(2)C(2)(CN)(2)](2)(-)). Reaction of AgNO(3), Na(2)(mnt) (mnt = maleonitriledithiolate, [S(2)C(2)(CN)(2)](2)(-)), and [2.2.2]-cryptand in acetonitrile yields [Na([2.2.2]-cryptand)](4)[Ag(4)(mnt)(4)].0.33MeCN (2). The Ag(4) anion of 2 is analogous to that in 1. Reaction of AgNO(3), Na(2)(mnt), and [NBu(4)]Br in acetonitrile yields [NBu(4)](4)[Ag(4)(mnt)(4)] (3). The anion of 3 also comprises an Ag(4) core coordinated by four mnt ligands, but the Ag(4) core is diamond-shaped rather than tetrahedral. Reaction of [K([2.2.2]-cryptand)](3)[Ag(mns)(Se(6))] with KNH(2) and [2.2.2]-cryptand in acetonitrile yields [K([2.2.2]-cryptand)](3)[Ag(mns)(2)].2MeCN (4). The anion of 4 comprises an Ag center coordinated by two mns ligands in a tetrahedral arrangement. Reaction of AgNO(3), 2 equiv of Na(2)(mnt), and [2.2.2]-cryptand in acetonitrile yields [Na([2.2.2]-cryptand)](3)[Ag(mnt)(2)] (5). The anion of 5 is analogous to that of 4. Electronic absorption and infrared spectra of each complex show behavior characteristic of metal-maleonitriledichalcogenates. Crystal data (153 K): 1, P2/n, Z = 2, a = 18.362(2) A, b = 16.500(1) A, c = 19.673(2) A, beta = 94.67(1) degrees, V = 5941(1) A(3); 2, P4, Z = 4, a= 27.039(4) A, c = 15.358(3) A, V = 11229(3) A(3); 3, P2(1)/c, Z = 6, a = 15.689(3) A, b = 51.924(11) A, c = 17.393(4) A, beta = 93.51(1) degrees, V = 14142(5) A(3); 4, P2(1)/c, Z = 4, a = 13.997(1) A, b = 21.866(2) A, c = 28.281(2) A, beta = 97.72(1) degrees, V = 8578(1) A(3); 5, P2/n, Z = 2, a = 11.547(2) A, b = 11.766(2) A, c = 27.774(6) A, beta = 91.85(3) degrees, V = 3772(1) A(3).     

Crown ethers as ancillary ligands in the assembly of silver(i) aggregates containing embedded acetylenediide

Five silver(I) double salts containing embedded acetylenediide, [Ag([12]crown-4)(2)][Ag(10)(C(2))(CF(3)CO(2))(9)([12]crown-4)(2)(H(2)O)(3)] x H(2)O (2), [Ag(2)C(2) x 5 AgCF(3)CO(2) x (benzo[15]crown-5) x 2 H(2)O] x 0.5 H(2)O (3), [Ag(4)([18]crown-6)(4)(H(2)O)(3)][Ag(18)(C(2))(3)(CF(3)CO(2))(16)(H(2)O)(2.5)] x 2.5 H(2)O (4), [Ag(2)C(2) x 6 AgC(2)F(5)CO(2) x 2([15]crown-5)](2) (5), and [(Ag(2)C(2))(2) x (AgC(2)F(5)CO(2))(9) x ([18]crown-6)(2) x (H(2)O)(3.5)] x H(2)O (6), have been isolated by varying the types of crown ethers and anions employed. Single-crystal X-ray analysis has shown that complex 2 is composed of winding anionic chains with sandwiched [Ag([12]crown-4)(2)](+) ions accommodated in the concave cavities between them. In 3, silver(I) double cages each sandwiched by a couple of benzo[15]crown-5 ligands are linked by [Ag(2)(CF(3)CO(2))(2)] bridges to form a one-dimensional structure. For 4, an anionic silver column is generated through fusion of two kinds of silver polyhedra (triangulated dodecahedron and bicapped trigonal antiprism), and the charge balance is provided by aqua-ligated [Ag([18]crown-6)](+) ions. Complex 5 is a centrosymmetric hexadecanuclear supermolecule composed of two [(eta(5)-[15]crown-5)(2)(C(2)@Ag(7))(mu-C(2)F(5)CO(2))(5)] moieties connected through a [Ag(2)(C(2)F(5)CO(2))(2)] bridge. Compound 6 is a discrete supermolecule containing an asymmetric (C(2))(2)@Ag(13) cluster core capped by two [18]crown-6 ligands in mu(3)-eta(5) and mu(4)-eta(6) ligation modes.     

Hybrid cluster-cages formed via cyanometalate condensation: Cs subset Co(4)Ru(6)S(2)(CN)(12), Co(4)Ru(9)S(6)(CN)(9), and Rh(4)Ru(9)S(6)(CN)(9) frameworks

Condensation of cyanometalates and cluster building blocks leads to the formation of hybrid molecular cyanometalate cages. Specifically, the reaction of [Cs subset [CpCo(CN)(3)](4)[CpRu](3)] and [(cymene)(2)Ru(3)S(2)(NCMe)(3)]PF(6) produced [Cs subset [CpCo(CN)(3)](4)[(cymene)(2)Ru(3)S(2)][CpRu](3)](PF(6))(2), Cs subset Co(4)Ru(6)S(2)(2+). Single-crystal X-ray diffraction, NMR spectroscopy, and ESI-MS measurements show that Cs subset Co(4)Ru(6)S(2)(2+ ) consists of a Ru(4)Co(4)(CN)(12) box fused with a Ru(3)S(2) cluster via a common Ru atom. The reaction of PPN[CpCo(CN)(3)] and 0.75 equiv of [(cymene)(2)(MeCN)(3)Ru(3)S(2)](PF(6))(2) in MeCN solution produced [[CpCo(CN)(3)](4)[(cymene)(2)Ru(3)S(2)](3)](PF(6))(2), Co(4)Ru(9)S(6)(2+). Crystallographic analysis, together with NMR and ESI-MS measurements, shows that Co(4)Ru(9)S(6)(2+ ) consists of a Ru(3)Co(4)(CN)(9) "defect box" core, wherein each Ru is fused to a Ru(3)S(2) clusters. The analogous condensation using [CpRh(CN)(3)](-) in place of [CpCo(CN)(3)](-) produced the related cluster-cage Rh(4)Ru(9)S(6)(2+). Electrochemical analyses of both Co(4)Ru(9)S(6)(2+) and Rh(4)Ru(9)S(6)(2+) can be rationalized in the context of reduction at the cluster and the Co(III) subunits, the latter being affected by the presence of alkali metal cations.     

Coordination polymers with carborane anions: silver dinitrile complexes

Crystalline materials have been isolated and characterized from mixing the silver carborane salts Ag(CB(11)H(12)) or Ag[Co(C(2)B(9)H(11))(2)] with nitrile ligands, either terminal acetonitrile or potentially bridging alkanedinitriles. Most of the complexes showed B-H...Ag interactions between the silver center and carborane anion. [Ag(acetonitrile)(2)(CB(11)H(12))] has a hexagonal network structure. [Ag(malonitrile)(2)(CB(11)H(12))] is a discrete dimeric complex, while [Ag(4)(succinonitrile)(5)(CB(11)H(12))(4)], [Ag(glutaronitrile)(2)][Co(C(2)B(9)H(12))(2)], and [Ag(glutaronitrile)[Co(C(2)B(9)H(11))(2)]] all show coordination chain structures. The carborane anions in [Ag(adiponitrile)[Co(C(2)B(9)H(11))(2)]] bridge between Ag centers to give a 3D CdSO(4)-related coordination polymer. The structure of [Ag(malonitrile)(2)](BF(4)) was also determined to have an unusual chiral diamondoid structure with a skewed 2-fold interpenetration.     

Heteroatomic molecular clusters derived from Group 15 Zintl ion cages: synthesis and isolation of [M2(HP7)2](2-) (M=Ag, Au), two novel cluster anions exhibiting metallophilic interactions

Ethylenediamine (en) solutions of K(3)P(7) and 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) were reacted with the homoleptic group 11 complexes [M(nbe)(3)][SbF(6)] (M = Ag, Au; nbe = norbornene) yielding two novel cluster anions, [M(2)(HP(7))(2)](2-), both of which were isolated in low crystalline yields as [K(2,2,2-crypt)](2)[M(2)(HP(7))(2)] (M = Ag (1) and Au (2)). Optimization of the reaction conditions by incorporation of a proton source (ammonium tetraphenylborate) and the replacement of the light-sensitive nbe adducts of silver and gold with the chloride salts MCl (M = Ag, Au) was found to greatly increase the yield and purity in which 1 and 2 were isolated. Compounds 1 and 2 were characterized by single crystal X-ray diffraction, electrospray ionization mass-spectrometry (ESI- MS), elemental analysis, and (1)H and (31)P NMR spectroscopy. Density functional theory (DFT) calculations on the cluster anions were also conducted.     

Synthesis, characterization, and chiral behavior of S-bridged Co(III)Pt(II)Co(III) trinuclear complexes composed of bis(thiolato)-type octahedral units cis(S)-[Co(aet)(2)(en)](+) and/or trans(N)-[Co(D-pen- N,O,S)(2)](-) (aet = 2-aminoethanethiolate, D-pen = D-penicillaminate)

A series of linear-type Co(III)Pt(II)Co(III) trinuclear complexes composed of C(2)-cis(S)-[Co(aet)(2)(en)](+) (aet = 2-aminoethanethiolate) and/or Lambda(D)-trans(N)-[Co(D-pen-N,O,S)(2)](-) (D-pen = D-penicillaminate) were newly prepared, and their chiral behavior, which is markedly different from that of the corresponding Co(III)Pd(II)Co(III) complexes, is reported. The 1:1 reaction of an S-bridged Co(III)Ni(II)Co(III) trinuclear complex, [Ni[Co(aet)(2)(en)](2)]Cl(4), with K(2)[PtCl(4)] in water gave an S-bridged Co(III)Pt(II)Co(III) trinuclear complex, [Pt[Co(aet)(2)(en)](2)]Cl(4) ([1]Cl(4)), while the corresponding 1:2 reaction produced an S-bridged Co(III)Pt(II) dinuclear complex, [PtCl(2)[Co(aet)(2)(en)]]Cl ([2]Cl). Complex [1](4+) formed both racemic (DeltaDelta/LambdaLambda) and meso (DeltaLambda) forms, which were separated and optically resolved by cation-exchange column chromatography. An optically active S-bridged Co(III)Pt(II)Co(III) trinuclear complex having the pseudo LambdaLambda configuration, Lambda(D)Lambda(D)-[Pt[Co(D-pen-N,O,S)(2)](2)](0) (Lambda(D)Lambda(D)-[3]), was also prepared by reacting Lambda(D)-trans(N)-K[Co(D-pen-N,O,S)(2)] with K(2)[PtCl(4)] in a ratio of 2:1 in water. Treatment of the racemic Delta/Lambda-[2]Cl with Lambda(D)-trans(N)-K[Co(D-pen-N,O,S)(2)] in a ratio of 1:1 in water led to the formation of LambdaLambda(D)- and DeltaLambda(D)-[Pt[Co(aet)(2)(en)][Co(D-pen-N,O,S)(2)]](2+) (LambdaLambda(D)- and DeltaLambda(D)-[4](2+)) and DeltaDelta(D)-[Pt[Co(aet)(2)(en)][Co(D-pen-N,S)(2)(H(2)O)(2)]](2+) (DeltaDelta(D)-[4'](2+)), besides trace amounts of Lambda(D)Lambda(D)-[3] and DeltaDelta- and DeltaLambda-[1](4+). These Co(III)Pt(II)Co(III) complexes were characterized on the basis of electronic absorption, CD, and NMR spectra, along with single-crystal X-ray analyses for DeltaDelta/LambdaLambda-[1]Cl(4), DeltaLambda-[1]Cl(4), and DeltaLambda(D)-[4]Cl(2). Crystal data: DeltaDelta/LambdaLambda-[1]Cl(4).6H(2)O, monoclinic, space group C2/c with a = 14.983(3) A, b = 19.857(4) A, c = 12.949(3) A, beta = 113.51(2) degrees, V = 3532(1) A(3), Z = 4; DeltaLambda-[1]Cl(4).3H(2)O, orthorhombic, space group Pbca with a = 14.872(3) A, b = 14.533(3) A, c = 14.347(2) A, V = 3100(1) A(3), Z = 4; DeltaLambda(D)-[4]Cl(2).6H(2)O, monoclinic, space group P2(1) with a = 7.3836(2) A, b = 20.214(1) A, c = 10.622(2) A, beta = 91.45(1) degrees V = 1682.0(4) A(3), Z = 2.