Construction of halide-bridged tungsten-copper-sulfide double cubanelike clusters from a new precursor [(Tp*WS2)2(μ-S2)

Treatment of [Et(4)N][Tp*WS(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS(2))(2)(μ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters [{Tp*W(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN)](2) (3), [{Tp*W(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)] (4), and [{Tp*W(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{Tp*W(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are linked via a μ(7)-Cl(-) bridge, two μ-Cl(-) bridges, and a [Cu(MeCN)(μ-Cl)(2)](+) bridge. For 4, one [Tp*W(μ(3)-S)(3)Cu(3)(MeCN)](2+) dication and one [Tp*W(μ(3)-S)(3)Cu(3)Br](+) cation are linked via a μ(4)-Br(-) and two μ-Br(-) bridges. For 5, the two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are bridged by a linear [(μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2)](4+) species. For 6 and 7, two [Tp*W(μ(3)-S)(3)Cu(3)X](+) cations are linked by a μ(4)-X(-) and two μ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.     

Bimetallic Ruthenium PNP Pincer Complex As a Platform to Model Proposed Intermediates in Dinitrogen Reduction to Ammonia

A series of ruthenium complexes was isolated and characterized in the course of reactions aimed at studying the reduction of hydrazine to ammonia in bimetallic systems. The diruthenium complex {[HPNPRu(N(2))](2)(μ-Cl)(2)}(BF(4))(2) (2) (HPNP = HN(CH(2)CH(2)P(i)Pr(2))(2)) reacted with 1 equiv of hydrazine to generate [(HPNPRu)(2)(μ(2)-H(2)NNH(2))(μ-Cl)(2)](BF(4))(2) (3) and with an excess of the reagent to form [HPNPRu(NH(3))(κ(2)-N(2)H(4))](BF(4))Cl (5). When phenylhydrazine was added to 2, the diazene species [(HPNPRu)(2)(μ(2)-HNNPh)(μ-Cl)(2)](BF(4))(2) (4) was obtained. Treatment of 2 with H(2) or CO yielded {[HPNPRu(H(2))](2)(μ-Cl)(2)}(BF(4))(2) (7) and [HPNPRuCl(CO)(2)]BF(4) (8), respectively. Abstraction of chloride using AgOSO(2)CF(3) or AgBPh(4) afforded the species [(HPNPRu)(2)(μ(2)-OSO(2)CF(3))(μ-Cl)(2)]OSO(2)CF(3) (9) and [(HPNPRu)(2)(μ-Cl)(3)]BPh(4) (10), respectively. Complex 3 reacted with HCl/H(2)O or HCl/Et(2)O to produce ammonia stoichiometrically; the complex catalytically disproportionates hydrazine to generate ammonia.     

Syntheses of chromium pentacarbonyl derivatives of arsenic(V) and antimony(V). contrasting chemical reactivity with organic halogen derivatives

We have synthesized a new series of chromium-group 15 dihydride and hydride complexes [H(2)As(Cr(CO)(5))(2)](-) (1) and [HE(Cr(CO)(5))(3)](2)(-) (E = As, 2a; E = Sb, 2b), which represent the first examples of group 6 complexes containing E-H fragments. The contrasting chemical reactivity of 2a and 2b with organic halogen derivatives is demonstrated. The reaction of 2a with RBr (R = PhCH(2), HC triple bond CCH(2)) produces the RX addition products [(R)(Br)As(Cr(CO)(5))(2)](-) (R = PhCH(2), 3; R = C(3)H(3), 4), while the treatment of 2b with RX (RX = PhCH(2)Br or HC triple bond CCH(2)Br, CH(3)(CH(2))(5)C(O)Cl) forms the halo-substituted complexes [XSb(Cr(CO)(5))(3)](2-) (X = Br, 5; X = Cl, 6). Moreover, the dihaloantimony complexes [XX'Sb(Cr(CO)(5))(2)](-) can be obtained from the reaction of 2b with the appropriate organic halides. In this study, a series of organoarsenic and antimony chromium carbonyl complexes have been synthesized and structurally characterized and the role of the main group on the formation of the resultant complexes is also discussed.     

Rhodium pyrazolate complexes as potential CVD precursors

Reaction of 3,5-(CF(3))(2)PzLi with [Rh(μ-Cl)(η(2)-C(2)H(4))(2)](2) or [Rh(μ-Cl)(PMe(3))(2)](2) in Et(2)O gave the dinuclear complexes [Rh(η(2)-C(2)H(4))(2)(μ-3,5-(CF(3))(2)-Pz)](2) (1) and [Rh(2)(μ-Cl)(μ-3,5-(CF(3))(2)-Pz) (PMe(3))(4)] (2) respectively (3,5-(CF(3))(2)Pz = bis-trifluoromethyl pyrazolate). Reaction of PMe(3) with [Rh(COD)(μ-3,5-(CF(3))(2)-Pz)](2) in toluene gave [Rh(3,5-(CF(3))(2)-Pz)(PMe(3))(3)] (3). Reaction of 1 and 3 in toluene (1?:?4) gave moderate yields of the dinuclear complex [Rh(PMe(3))(2)(μ-3,5-(CF(3))(2)-Pz)](2) (4). Reaction of 3,5-(CF(3))(2)PzLi with [Rh(PMe(3))(4)]Cl in Et(2)O gave the ionic complex [Rh(PMe(3))(4)][3,5-(CF(3))(2)-Pz] (5). Two of the complexes, 1 and 3, were studied for use as CVD precursors. Polycrystalline thin films of rhodium (fcc-Rh) and metastable-amorphous films of rhodium phosphide (Rh(2)P) were grown from 1 and 3 respectively at 170 and 130 °C, 0.3 mmHg in a hot wall reactor using Ar as the carrier gas (5 cc min(-1)). Thin films of amorphous rhodium and rhodium phosphide (Rh(2)P) were grown from 1 and 3 at 170 and 130 °C respectively at 0.3 mmHg in a hot wall reactor using H(2) as the carrier gas (7 cc min(-1)).     

Reactions of the tetrafluoroborate complex [Mo2Cp2(κ(2)-F2BF2)(μ-PPh2)2(CO)]BF4 with mono- and bidentate ligands having E-H bonds (E = O, S, Se, N, P)

The title compound reacted rapidly with CN(t)Bu at room temperature by displacing the BF(4)(-) ligand and incorporating three molecules of isocyanide to yield the electron-precise complex [Mo(2)Cp(2)(μ-PPh(2))(2)(CN(t)Bu)(3)(CO)](BF(4))(2), which was obtained as a mixture of cis and trans isomers. Reaction with several HER(n) molecules (HER(n) = HSPh, HSePh, H(2)PCy) took place with formal elimination of HBF(4) and spontaneous carbonylation to give the electron-precise cations [Mo(2)Cp(2)(μ-ER(n))(μ-PPh(2))(2)(CO)(2)](+). Reactions with several bidentate ligands (L(2)H) having acidic E-H bonds (2-hydroxypyridine, 2-mercaptopyridine, cathecol, 2-aminophenol, and 2-aminothiophenol) proceeded analogously with deprotonation of these bonds with the preference E = S > O > N. The N,O-donor ligands yielded 32-electron chelate derivatives of the type [Mo(2)Cp(2)(O,N-L(2))(μ-PPh(2))(2)(CO)]BF(4) (L(2) = OC(5)H(4)N, OC(6)H(4)NH(2)), whereas the S,N-donors yielded 34-electron, S-bridged complexes [Mo(2)Cp(2)(μ-S:S,N-L(2))(μ-PPh(2))(2)(CO)]BF(4) [L(2) = SC(5)H(4)N (Mo-Mo = 2.8895(8) ?), SC(6)H(4)NH(2)]. However, reaction with catechol gave a monodentate derivative [Mo(2)Cp(2)(O-OC(6)H(4)OH)(μ-PPh(2))(2)(CO)]BF(4). In contrast, reactions of the title complex with several carboxylic acids and related species (acetic, benzoic, and thioacetic acids, acetamide, thioacetamide, and sodium diethyldithiocarbamate) were insensitive to the nature of the donor atoms and gave in all cases 32-electron chelate derivatives of type [Mo(2)Cp(2)(κ(2)-L(2))(μ-PPh(2))(2)(CO)]BF(4). All of the above cations having Mo-bound OH, NH, or NH(2) groups were easily deprotonated upon reaction with 1,8-diazabicycloundec-7-ene (DBU) or other bases to give neutral complexes which exhibited different coordination motifs depending on the donor atoms, including chelate complexes of the type [Mo(2)Cp(2)(κ(2)-L(2)')(μ-PPh(2))(2)(CO)] (L(2)' = OC(6)H(4)O, OC(6)H(4)NH), the bridged complexes [Mo(2)Cp(2)(μ-S,N:S,N-SC(6)H(4)NH)(μ-PPh(2))(2)] and [Mo(2)Cp(2){μ-S,N-N(S)CMe}(μ-PPh(2))(2)], and the terminal acetylimido complex [Mo(2)Cp(2){N-N(O)CMe}(μ-PPh(2))(2)(CO)].     

Unexpected multiple bond cleavage and rearrangement of organosulfide ligands in the presence of Cu(II) assisted by solvothermal and solvothermal-microwave conditions

An unprecedented in situ multiple bond cleavage of S-S, S-C(sp(2)) and C-N in the pyrimidinedisulfide (pym(2)S(2)) ligand is observed by the reaction of CuCl(2)·2H(2)O with this ligand under solvothermal and solvothermal-microwave conditions. In this process the formation of the compound [Cu(II)(μ-Cl)(Cl)L](2), where L represents the new ligand (L = 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde), is observed. This ligand has been further isolated and X-ray characterized. The similar reaction carried out under solvothermal-microwave conditions gives, in addition to the latter compound, the complex {9·[Cu(pym(2)S(3))(μ-Cl)(Cl)](2)·[Cu(pym(2)S(2))(μ-Cl)(Cl)](2)}. Coordination of a pyrimidinetrisulfide ligand (pym(2)S(3)) is reported for the first time. This work represents an illustrative example of the novel synthetic perspectives attainable via solvothermal-microwave procedures.     

Nickel poly-acetylide carbonyl clusters: structural features, bonding and electrochemical behaviour

The reactions of [NEt(4)](2)[Ni(6)(CO)(12)] with miscellaneous carbon halides (e.g. CCl(4), C(4)Cl(6)) in CH(2)Cl(2) have been extensively investigated particularly focusing on the stoichiometric ratio of the reagents and reaction temperature. This allowed the preparation of the previously known acetylide clusters [Ni(16)(C(2))(2)(CO)(23)](4-), [HNi(25)(C(2))(4)(CO)(32)](3-) and [Ni(22)(C(2))(4)(CO)(28)Cl](3-), as well as isolation and full characterisation of the closely related [Ni(17)(C(2))(2)(CO)(24)](4-) and [Ni(25)(C(2))(4)(CO)(32)](4-) tetraanions. From a structural point of view, all these clusters are based on a Ni(16) square orthobicupola which contain interstitial C(2), Ni(η(2)-C(2))(4) or Ni(2)(μ-η(2)-C(2))(4) moieties, displaying rather short C-C bonds. Electrochemical studies reveal that all these species undergo different redox processes, even if their stability is rather limited. This is corroborated by an extensive analysis of the interaction between interstitial C(2) acetylide units and the metal cluster cage by Extended Huckel Molecular Orbital (EHMO) calculations, which indicates that tightly bonded C-C units are less effective than isolated C-atoms in stabilising the cluster cage.     

How to make a major shift in a redox potential: ligand control of the oxidation state of dimolybdenum units

A compound reported earlier (Polyhedron 1989, 8, 2339) as (Bu(n)()(4)N)(2)H(2)[Mo(2)[Mo(CO)(4)(PhPO(2))(2)](2)] has been reexamined. We find that the hydrogen atoms in this formula are not present. Therefore, the complex must be considered as having a central triply bonded Mo(2)(6+) unit, instead of a quadruply bonded Mo(2)(4+) unit. Our conclusion is based on a variety of experimental evidence, including X-ray crystal structures of four crystal forms, as well as the neutron crystal structure of one. This explains the relatively long Mo-Mo bond lengths found in the range 2.1874(7)-2.2225(7) A and the absence of a delta --> delta transition in the visible spectrum. From electrochemistry we also find that the diphosphonate ligand has such an exceptional ability to stabilize higher oxidation states that even common solvents such as CH(2)Cl(2) and C(2)H(5)OH readily oxidize the Mo(2)(4+) unit that is introduced from the Mo(2)(O(2)CCH(3))(4) or [Mo(2)(O(2)CCH(3))(2)(NCCH(3))(6)](BF(4))(2) employed in the preparation. The only chemically reversible wave at E(1/2) = -1.54 V vs Ag/AgCl corresponds to the reduction process Mo(2)(6+) --> Mo(2)(5+).     

Transition metal complexes of the novel hexadentate ligand 1,4-bis(di(N-methylimidazol-2-yl)methyl)phthalazine

The novel polydentate ligand 1,4-bis(di(N-methylimidazol-2-yl)methyl)phthalazine, bimptz, has been synthesized and its coordination chemistry was investigated. Bimptz is neutral and contains a central phthalazine unit, to which two di-(N-methylimidazol-2-yl)methyl groups are attached in the 1,4-positions. This ligand therefore provides up to 6 donor sites for coordination to metal ions. A series of metal complexes of bimptz was prepared and their molecular structures were determined by X-ray diffraction. Upon reaction of bimptz with two equivalents of MnCl(2)·4H(2)O, CoCl(2)·6H(2)O and [Ru(dmso)(4)Cl(2)], the dinuclear complexes [Mn(2)(bimptz)(μ-Cl)(2)Cl(2)] (1), [Co(2)(bimptz)(CH(3)OH)(2)(μ-Cl)(2)](PF(6))(2) (3) and [Ru(2)(bimptz)(dmso)(2)(μ-Cl)(2)](PF(6))(2) (4), respectively, were isolated. The latter were found to have similar solid state structures with octahedrally coordinated metal centers bridged by the phthalazine unit and two chloro ligands. The cobalt and ruthenium complexes 3 and 4 were isolated as PF(6)(-) salts and contain neutral methanol and dmso ligands, respectively, at the terminal coordination sites of the metal centres. The mononuclear ruthenium complex [Ru(Hbimptz)(2)](PF(6))(4) (6) was obtained from the reaction of two equivalents bimptz with [Ru(dmso)(4)Cl(2)]. In complex 6, three donor sites per ligand molecule are used for coordination of the Ru(ii) center. In each bimptz ligand, one of the remaining, dangling N-methylimidazole rings is protonated and forms a hydrogen bond with the unprotonated N-methylimidazole ring of the other bimptz ligand.     

Synthesis and structure of a bismuth(III)/chromium(VI) oxo cluster containing a Bi4Cr4O12 core

Bismuth(III) compounds containing the Kl?ui's oxygen tripodal ligand [CpCo{P(O)(OEt)(2)}(3)](-) (L(OEt)(-)) have been synthesized, and their interactions with dichromate in aqueous media were studied. The treatment of Bi(5)O(OH)(9)(NO(3))(4) with NaL(OEt) in water afforded [L(OEt)Bi(NO(3))(2)](2) (1), whereas that of BiCl(3) with NaL(OEt) in CH(2)Cl(2) yielded L(OEt)BiCl(2) (2). Chloride abstraction of 2 with AgX afforded [L(OEt)BiX(2)](2) [X(-) = triflate (OTf(-)) (3), tosylate (OTs(-)) (4)]. In aqueous solutions at pH > 4, 4 underwent ligand redistribution to give the bis(tripod) complex [(L(OEt))(2)Bi(H(2)O)][OTs] (5). The treatment of 4 with Na(2)Cr(2)O(7) in acetone/water afforded the Bi(III)/Cr(VI) oxo cluster [(L(OEt))(4)Bi(4)(μ(3)-CrO(4))(2)(μ(3)-Cr(2)O(7))(2)] (6) containing a unique Bi(4)Cr(4)O(12) oxometallic core. Compound 6 oxidized benzyl alcohol to give ca. 6 equiv of benzaldehyde. The reaction between 2 and CrO(3) yielded [L(OEt)Bi(OCrO(2)Cl)](2)(μ-Cl)(2) (7). The crystal structures of complexes 4-7 have been determined.     

Multiple silicon-hydrogen bond activations at adjacent rhodium and iridium centers

The reaction of 1 equiv of primary silanes, SiH(3)R (R = Ph, Mes), with [RhIr(CO)(3)(dppm)(2)] yields mono(silylene)-bridged complexes of the type [RhIr(H)(2)(CO)(2)(μ-SiHR)(dppm)(2)] (R = Ph or Mes), while for R = Ph the addition of 2 equiv yields the bis(silylene)-bridged complexes, [RhIr(CO)(2)(μ-SiHPh)(2)(dppm)(2)]. The kinetic isomer of this bis(silylene)-bridged product has the phenyl substituent axial on one silylene unit and equatorial on the other, and in the presence of excess silane this rearranges to the thermodynamically preferred "axial-axial" isomer, in which the phenyl substituents on each bridging silylene unit are axial and parallel to one another. The reaction of 1 equiv of diphenylsilane with [RhIr(CO)(3)(dppm)(2)] produces the mono(silylene)-bridged product, [RhIr(H)(2)(CO)(2)(μ-SiPh(2))(dppm)(2)], and the subsequent addition of silane in the presence of CO yields the silyl/silylene product [RhIr(H)(SiPh(2)H)(CO)(3)(κ(1)-dppm)(μ-SiPh(2))(dppm)]. The reaction of [RhIr(CO)(3)(dppm)(2)] with 2 equiv of SiH(2)Me(2) yields the analogous product [RhIr(H)(SiMe(2)H)(CO)(3)(κ(1)-dppm)(μ-SiMe(2))(dppm)]. Low-temperature NMR spectroscopic observation of some key intermediates, such as [RhIr(H)(SiH(2)Ph)(CO)(2)(μ-CO)(dppm)(2)], formed during the formation of the mono(silylene)-bridged species provides evidence for a mechanism involving initial Si-H bond activation at Rh, followed by the subsequent Si-H bond activation at Ir. The Si-H bond activation of a second equivalent of silane seems to be initiated by dissociation of the Rh-bound end of one diphosphine. The reaction of diphenylsilane with the cationic complex [RhIr(CH(3))(CO)(2)(dppm)(2)][CF(3)SO(3)] gives rise to a different reactivity pattern in which Si-H bond activation is initiated at Ir. In this case, the cationic silyl-bridged species, [RhIr(CH(3))(CO)(2)(κ(1):η(2)-SiHPh(2))(dppm)(2)][CF(3)SO(3)], contains an agostic Si-H interaction with Rh. In solution, at ambient temperature, this complex converts to two species, [RhIr(H)(COCH(3))(CO)(μ-H)(μ-SiPh(2))(dppm)(2)][CF(3)SO(3)] and [RhIr(CO)(2)(μ-H)(μ-SiPh(2))(dppm)(2)] [CF(3)SO(3)], formed by the competing methyl migration to CO and reductive elimination of methane, respectively. In the diphenylsilylene dihydride product, a weak interaction between the bridging silicon and the terminal Ir-bound hydride is proposed on the basis of NMR evidence.     

Synthesis and reactivity of W3Te74+ clusters and chalcogen exchange in the M3Q7 (M = Mo, W; Q = S, Se, Te) cluster family

Heating WTe(2), Te, and Br(2) at 390 degrees C followed by extraction with KCN gives [W(3)Te(7)(CN)(6)](2-). Crystal structures of double salts Cs(3.5)K{[W(3)Te(7)(CN)(6)]Br}Br(1.5).4.5H(2)O (1), Cs(2)K(4){[W(3)Te(7)(CN)(6)](2)Cl}Cl.5H(2)O (2), and (Ph(4)P)(3){[W(3)Te(7)(CN)(6)]Br}.H(2)O (3) reveal short Te(2)...X (X = Cl, Br) contacts. Reaction of polymeric Mo(3)Se(7)Br(4) with KNCSe melt gives [Mo(3)Se(7)(CN)(6)](2-). Reactions of polymeric Mo(3)S(7)Br(4) and Mo(3)Te(7)I(4) with KNCSe melt (200-220 degrees C) all give as final product [Mo(3)Se(7)(CN)(6)](2)(-) via intermediate formation of [Mo(3)S(4)Se(3)(CN)(6)](2-)/[Mo(3)SSe(6)(CN)(6)](2-) and of [Mo(3)Te(4)Se(3)(CN)(6)](2-), respectively, as was shown by ESI-MS. (NH(4))(1.5)K(3){[Mo(3)Se(7)(CN)(6)]I}I(1.5).4.5H(2)O (4) was isolated and structurally characterized. Reactions of W(3)Q(7)Br(4) (Q = S, Se) with KNCSe lead to [W(3)Q(4)(CN)(9)](5-). Heating W(3)Te(7)Br(4) in KCNSe melt gives a complicated mixture of W(3)Q(7) and W(3)Q(4) derivatives, as was shown by ESI-MS, from which E(3)[W(3)(mu(3)-Te)(mu-TeSe)(3)(CN)(6)]Br.6H(2)O (5) and K(5)[W(3)(mu(3)-Te)(mu-Se)(3)(CN)(9)] (6) were isolated. X-ray analysis of 5 reveals the presence of a new TeSe(2-) ligand. The complexes were characterized by IR, Raman, electronic, and (77)Se and (125)Te NMR spectra and by ESI mass spectrometry.     

Organoplatinum(II) complexes containing chelating or bridging bis(N-heterocyclic carbene) ligands: formation of a platinum(II) carbonate complex by aerial CO2 fixation

The preparation of two new bis(N-heterocyclic carbene) platinum(II) complexes, in which NHC rings are joined by a CH(2) linker group, is described. While, the chelate complex [PtMe(2)(bis-NHC1)], 1, was formed with large tert-butyl wingtips, the iso-propyl N-substituent analogue favors formation of the cluster complex [Pt(2)Me(4)(μ-SMe(2))(μ-bis-NHC2)](2)(μ-Ag(2)Br(2)), 2, in which two binuclear platinum(II) complexes are linked together by an Ag(2)Br(2) unit. The chelating platinum complex 1 undergoes aerial CO(2) fixation and forms platinum(II) carbonate complex [Pt(CO(3))(bis-NHC1)], 3.     

Copper halide-bridged ruthenium telluride carbonyl complexes: discovery of the semiconducting cluster chain polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2].THF}infinity

A new series of Te-Ru-Cu carbonyl complexes was prepared by the reaction of K(2)TeO(3) with [Ru(3)(CO)(12)] in MeOH followed by treatment with PPh(4)X (X=Br, Cl) and [Cu(MeCN)(4)]BF(4) or CuX (X=Br, Cl) in MeCN. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was first treated with PPh(4)X followed by the addition of [Cu(MeCN)(4)]BF(4), doubly CuX-bridged Te(2)Ru(4)-based octahedral clusters [PPh(4)](2)[Te(2)Ru(4)(CO)(10)Cu(2)X(2)] (X=Br, [PPh(4)](2)[1]; X=Cl, [PPh(4)](2)[2]) were obtained. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)X (X=Br, Cl) followed by the addition of CuX (X=Br, Cl), three different types of CuX-bridged Te-Ru carbonyl clusters were obtained. While the addition of PPh(4)Br or PPh(4)Cl followed by CuBr produced the doubly CuBr-bridged cluster 1, the addition of PPh(4)Cl followed by CuCl led to the formation of the Cu(4)Cl(2)-bridged bis-TeRu(5)-based octahedral cluster compound [PPh(4)](2)[{TeRu(5)(CO)(14)}(2)Cu(4)Cl(2)] ([PPh(4)](2)[3]). On the other hand, when the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te(2)Ru(4)-based octahedral cluster chain polymer {[PPh(4)](2)(Te(2)Ru(4)(CO)(10)Cu(4)Br(2)Cl(2)).THF}(infinity) ({[PPh(4)](2)[4].THF}(infinity)) was produced. The chain polymer {[PPh(4)](2)[4].THF}(infinity) is the first ternary Te-Ru-Cu cluster and shows semiconducting behavior with a small energy gap of about 0.37 eV. It can be rationalized as resulting from aggregation of doubly CuX-bridged clusters 1 and 2 with two equivalents of CuCl or CuBr, respectively. The nature of clusters 1-4 and the formation and semiconducting properties of the polymer of 4 were further examined by molecular orbital calculations at the B3LYP level of density functional theory.     

Electronic structures of ruthenium and osmium complexes of 9,10-phenanthrenequinone

The reaction of 9,10-phenanthrenequinone (PQ) with [M(II)(H)(CO)(X)(PPh(3))(3)] in boiling toluene leads to the homolytic cleavage of the M(II)-H bond, affording the paramagnetic trans-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 1; M = Os, X = Br, 3) and cis-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 2; M = Os, X = Br, 4) complexes. Single-crystal X-ray structure determinations of 1, 2·toluene, and 4·CH(2)Cl(2), EPR spectra, and density functional theory (DFT) calculations have substantiated that 1-4 are 9,10-phenanthrenesemiquinone radical (PQ(?-)) complexes of ruthenium(II) and osmium(II) and are defined as trans-[Ru(II)(PQ(?-))(PPh(3))(2)(CO)Cl] (1), cis-[Ru(II)(PQ(?-))(PPh(3))(2)(CO)Cl] (2), trans-[Os(II)(PQ(?-))(PPh(3))(2)(CO) Br] (3), and cis-[Os(II)(PQ(?-))(PPh(3))(2)(CO)Br] (4). Two comparatively longer C-O [average lengths: 1, 1.291(3) ?; 2·toluene, 1.281(5) ?; 4·CH(2)Cl(2), 1.300(8) ?] and shorter C-C lengths [1, 1.418(5) ?; 2·toluene, 1.439(6) ?; 4·CH(2)Cl(2), 1.434(9) ?] of the OO chelates are consistent with the presence of a reduced PQ(?-) ligand in 1-4. A minor contribution of the alternate resonance form, trans- or cis-[M(I)(PQ)(PPh(3))(2)(CO)X], of 1-4 has been predicted by the anisotropic X- and Q-band electron paramagnetic resonance spectra of the frozen glasses of the complexes at 25 K and unrestricted DFT calculations on 1, trans-[Ru(PQ)(PMe(3))(2)(CO)Cl] (5), cis-[Ru(PQ)(PMe(3))(2)(CO)Cl] (6), and cis-[Os(PQ)(PMe(3))(2)(CO)Br] (7). However, no thermodynamic equilibria between [M(II)(PQ(?-))(PPh(3))(2)(CO)X] and [M(I)(PQ)(PPh(3))(2)(CO)X] tautomers have been detected. 1-4 undergo one-electron oxidation at -0.06, -0.05, 0.03, and -0.03 V versus a ferrocenium/ferrocene, Fc(+)/Fc, couple because of the formation of PQ complexes as trans-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (1(+)), cis-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (2(+)), trans-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (3(+)), and cis-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (4(+)). The trans isomers 1 and 3 also undergo one-electron reduction at -1.11 and -0.96 V, forming PQ(2-) complexes trans-[Ru(II)(PQ(2-))(PPh(3))(2)(CO)Cl](-) (1(-)) and trans-[Os(II)(PQ(2-))(PPh(3))(2)(CO)Br](-) (3(-)). Oxidation of 1 by I(2) affords diamagnetic 1(+)I(3)(-) in low yields. Bond parameters of 1(+)I(3)(-) [C-O, 1.256(3) and 1.258(3) ?; C-C, 1.482(3) ?] are consistent with ligand oxidation, yielding a coordinated PQ ligand. Origins of UV-vis/near-IR absorption features of 1-4 and the electrogenerated species have been investigated by spectroelectrochemical measurements and time-dependent DFT calculations on 5, 6, 5(+), and 5(-).     

Halide and nitrite recognizing hexanuclear metallacycle copper(II) pyrazolates

Halide-centered hexanuclear, anionic copper(II) pyrazolate complexes [trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)X](-), X = Cl, Br, I are isolated in a good yield from the redox reaction of the trinuclear copper(I) pyrazolate complex [μ-Cu(3)((3,5-CF(3))(2)pz)(3)] with a halide source such as PPh(3)AuCl or [Bu(4)N]X, X = Cl, Br, or I, in air. X-ray structures of the anion-centered hexanuclear complexes show that the six copper atoms are bridged by bis(3,5-trifluoromethyl)pyrazolate and hydroxyl ligands above and below the six copper atom plane. The anions are located at the center of the cavity and weakly bound to the six copper atoms in a μ(6)-arrangement, Cu-X = ~3.1 ?. A nitrite-centered hexanuclear copper(II) pyrazolate complex [trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)(NO(2))](-) was obtained when a solution of [PPN]NO(2) in CH(3)CN was added dropwise to the trinuclear copper(I) pyrazolate complex [μ-Cu(3)((3,5-CF(3))(2)pz)(3)] dissolved in CH(3)CN, in air. Blue crystals are produced by slow evaporation of the acetonitrile solvent. The X-ray structure of [PPN][trans-Cu(6)((3,5-CF(3))(2)pz)(6)(OH)(6)(NO(2))] complex shows the nitrite anion sits in the hexanuclear cavity and is perpendicular to the copper plane with a O-N-O angle of 118.3(7)°. The (19)F and (1)H NMR of the pyrazolate ring atoms are sensitive to the anion present in the ring. Anion exchange of the NO(2)(-) by Cl(-) can be observed easily by (1)H NMR.     

Unusual ligand transformations initiated by dppm deprotonation in methylene-bridged Rh/Os complexes

The reaction of [RhOs(CO)(3)(μ-CH(2))(dppm)(2)][CF(3)SO(3)] (dppm = μ-Ph(2)PCH(2)PPh(2)) with 1,3,4,5-tetramethylimidazol-2-ylidene (IMe(4)) results in competing substitution of the Rh-bound carbonyl by IMe(4) and dppm deprotonation by IMe(4) to give the two products [RhOs(IMe(4))(CO)(2)(μ-CH(2))(dppm)(2)][CF(3)SO(3)] and [RhOs(CO)(3)(μ-CH(2))(μ-κ(1):η(2)-dppm-H)(dppm)] [3; dppm-H = bis(diphenylphosphino)methanide], respectively. In the latter product, the dppm-H group is P-bound to Os while bound to Rh by the other PPh(2) group and the adjacent methanide C. The reaction of the tetracarbonyl species [RhOs(CO)(4)(μ-CH(2))(dppm)(2)][CF(3)SO(3)] with IMe(4) results in the exclusive deprotonation of a dppm ligand to give [RhOs(CO)(4)(μ-CH(2))(μ-κ(1):κ(1)-dppm-H)(dppm)] (4) in which dppm-H is P-bound to both metals. Both deprotonated products are cleanly prepared by the reaction of their respective precursors with potassium bis(trimethylsilyl)amide. Reversible conversion of the μ-κ(1):η(2)-dppm-H complex to the μ-κ(1):κ(1)-dppm-H complex is achieved by the addition or removal of CO, respectively. In the absence of CO, compound 3 slowly converts in solution to [RhOs(CO)(3)(μ-κ(1):κ(1):κ(1)-Ph(2)PCHPPh(2)CH(2))(dppm)] (5) as a result of dissociation of the Rh-bound PPh(2) moiety of the dppm-H group and its attack at the bridging CH(2) group. Compound 4 is also unstable, yielding the ketenyl- and ketenylidene/hydride tautomers [RhOs(CO)(3)(μ-κ(1):η(2)-CHCO)(dppm)(2)] (6a) and [RhOs(H)(CO)(3)(μ-κ(1):κ(1)-CCO)(dppm)(2)] (6b), initiated by proton transfer from μ-CH(2) to dppm-H. Slow conversion of these tautomers to a pair of isomers of [RhOs(H)(CO)(3)(μ-κ(1):κ(1):κ(1)-Ph(2)PCH(COCH)PPh(2))(dppm)] (7a and 7b) subsequently occurs in which proton transfer from a dppm group to the ketenylidene fragment gives rise to coupling of the resulting dppm-H methanide C and the ketenyl unit. Attempts to couple the ketenyl- or ketenylidene-bridged fragments in 6a/6b with dimethyl acetylenedicarboxylate (DMAD) yield [RhOs(κ(1)-CHCO)(CO)(3)(μ-DMAD)(dppm)(2)], in which the ketenyl group is terminally bound to Os.     

Aqueous Solution Chemistry of the Mo(3)PdS(4) Cube: Substitution Reactions and the Double to Single Cube Interconversion Induced by CO, Two Phosphines, Cl(-), Br(-), and NCS(-)

The kinetics of conversion of an edge-linked double cube, in this case [{Mo(3)PdS(4)(H(2)O)(9)}(2)](8+), to the corresponding single cube [Mo(3)(PdX)S(4)(H(2)O)(9)](4+), has been studied for the first time. Reaction is induced by six reagents X = CO, two water-soluble phosphines, Cl(-), Br(-), and NCS(-), which complex at the tetrahedral Pd. The first stage of reaction is fast and is accompanied by color changes, e.g. purple to dark blue in the case of Cl(-), assigned as double to single cube conversion. With X = CO and the two phosphines, when absorbance changes are intense enough for stopped-flow monitoring with reactants at Pd-SCN. On removal of e.g. Cl(-) by chromatography or addition of Ag(+), the double cube re-forms.     

Dinuclear silver(I) complexes for the design of metal-ligand networks based on triazolopyrimidines

Silver(I) coordination complexes with the versatile and biomimetic ligands 1,2,4-triazolo[1,5-a]pyrimidine (tp), 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine (dmtp) and 7-amine-1,2,4-triazolo[1,5-a]pyrimidine (7atp) all feature dinuclear [Ag(2)(μ-tp)(2)](2+) building units (where tp is a triazolopyrimidine derivative), which are the preferred motif, independently of the counter-anion used. According to AIM (atoms in molecules) and ELF (electron localization function) analyses, this fact is due to the great stability of these dinuclear species. The complexes structures range from the dinuclear entities [Ag(2)(μ-tp)(2)(CH(3)CN)(4)](BF(4))(2) (1), [Ag(2)(μ-tp)(2)(CH(3)CN)(4)](ClO(4))(2) (2), [Ag(2)(μ-7atp)(2)](ClO(4))(2) (3) and [Ag(2)(μ-dmtp)(2)(CH(3)CN)](PF(6))(ClO(4)) (4) over the 1D polymer chain [Ag(2)(μ-CF(3)SO(3))(2)(μ-dmtp)(2)](n) (5) to the 3D net {[Ag(2)(μ(3)-tp)(2)](PF(6))(2)·～6H(2)O}(n) (6) with NbO topology.     

A diruthenium soft ferromagnet showing T(c) = 3.0 K: Mn4(H2O)16H[Ru2(CO3)4]2[Ru2(CO3)4(H2O)2]·11H2O

A three-dimensional CO(3)(2-)-bridged Mn(II)-Ru(2)(II,III) complex, Mn(4)(H(2)O)(16)H[Ru(2)(CO(3))(4)](2)[Ru(2)(CO(3))(4)(H(2)O)(2)]·11H(2)O (1), was synthesized by self-assembling Ru(2)(CO(3))(4)(3-) paddle-wheel precursors and Mn(2+) cations. It contains an unprecedented layer [Ru(2)(CO(3))(4)](n)(3n-) with (4,4) network. The ferromagnetic coupling between spin centers results in ordering below 3.0 K.