Different modes of aggregation in organoaluminium and -gallium hydroxylamides

The organoaluminium and -gallium hydroxylamides (Me2GaONMe2)2, (tBu2AlONMe2)2, (tBu2GaONMe2)2 and (Me2AlONiPr2)2 have been prepared by the reaction of the hydroxylamines Me2NOH and iPr2NOH with the trialkylmetal compounds trimethylgallium, tri-tbutylaluminium and tri-tbutylgallium, respectively. All compounds have been characterised by NMR spectroscopy (1H, 13C, 15N, 17O and 27Al), by mass spectrometry and elemental analyses. The crystal structures of the four compounds have been determined, showing that they all form dimers but with different modes of aggregation: (Me2GaONMe2)2 has a Ga2O2N2 six-membered ring, (tBu2AlONMe2)2 and (Me2AlONiPr2)2 have Al2O2 four-membered rings, (tBu2GaONMe2)2 forms a Ga2O2N five-membered ring.     

Synthesis and catalytic epoxidation activity with TBHP and H2O2 of dioxo-, oxoperoxo-, and oxodiperoxo molybdenum(VI) and tungsten(VI) compounds containing monodentate or bidentate phosphine oxide ligands: crystal structures of WCl2(O)2(OPMePh2)2, WCl2(O)(O2)(OPMePh2)2, MoCl2(O)2dppmO2.C4H10O, WCl2(O)2dppmO2, Mo(O)(O2)2dppmO2, and W(O)(O2)2dppmO2

The dioxo tungsten(VI) and molybdenum(VI) complexes WCl2(O)2(OPMePh2)2, WCl2(O)2dppmO2, and MoCl2(O)2dppmO2, the oxoperoxo compounds WCl2(O)(O2)(OPMePh2)2, WCl2(O)(O2)dppmO2, and MoCl2(O)(O2)dppmO2, and the oxodiperoxo complexes, W(O)(O2)2dppmO2 and Mo(O)(O2)2dppmO2 have been prepared and characterized by IR spectroscopy, 31P NMR spectroscopy, elemental analysis, and X-ray crystallography. The structural and X-ray crystallographic data of compounds WCl2(O)2(OPMePh2)2, WCl2(O)(O2)(OPMePh2)2, MoCl2(O)2dppmO2.4H10O, WCl2(O)2dppmO2, Mo(O)(O2)2dppmO2, and W(O)(O2)2dppmO2 are also detailed. All complexes were studied as catalysts for cis-cyclooctene epoxidation in the presence of tert-butyl hydroperoxide (TBHP) or H2O2 as an oxidant. The Mo-based catalysts showed a superior reactivity over W-based catalysts in the TBHP system. On the other hand, in the H2O2 system, the W-based catalysts (accomplishing nearly 100% epoxidation of cyclooctene in 6 h) are more reactive than the Mo catalysts (<45% under some conditions). Various solvent systems have been investigated, and ethanol is the most suitable solvent for the H2O2 system.     

Binuclear iron-sulfur complexes with bidentate phosphine ligands as active site models of Fe-hydrogenase and their catalytic proton reduction

The displacement of CO in a few simple Fe(I)-Fe(I) hydrogenase model complexes by bisphosphine ligands Ph2P-(CH2)n-PPh2 [with n = 1 (dppm) or n = 2 (dppe)] is described. The reaction of [{mu-(SCH2)2CH2}Fe2(CO)6] (1) and [{mu-(SCH2)2N(CH2CH2CH3)}Fe2(CO)6] (2) with dppe gave double butterfly complexes [{mu-(SCH2)2CH2}Fe2(CO)5(Ph2PCH2)]2 (3) and [{mu-(SCH2)2N(CH2CH2CH3)}Fe2(CO)5(Ph2PCH2)]2 (4), where two Fe2S2 units are linked by the bisphosphine. In addition, an unexpected byproduct, [{mu-(SCH2)2N(CH2CH2CH3)}Fe2(CO)5{Ph2PCH2CH2(Ph2PS)}] (5), was isolated when 2 was used as a substrate, where only one phosphorus atom of dppe is coordinated, while the other has been converted to P=S, presumably by nucleophilic attack on bridging sulfur. By contrast, the reaction of 1 and 2 with dppm under mild conditions gave only complexes [{mu-(SCH2)2CH2}Fe2(CO)5(Ph2PCH2PPh2)] (6) and [{mu-(SCH2)2N(CH2CH2CH3)}Fe2(CO)5(Ph2PCH2PPh2)] (8), where one ligand coordinated in a monodentate fashion to one Fe2S2 unit. Furthermore, under forcing conditions, the complexes [{mu-(SCH2)2CH2}Fe2(CO)4{mu-(Ph2P)2CH2}] (7) and [{mu-(SCH2)2N(CH2CH2CH3)}Fe2(CO)4{mu-(Ph2P)2CH2}] (9) were formed, where the phosphine acts as a bidentate ligand, binding to both the iron atoms in the same molecular unit. Electrochemical studies show that the complexes 3, 4, and 9 catalyze the reduction of protons to molecular hydrogen, with 4 electrolyzed already at -1.40 V versus Ag/AgNO3 (-1.0 V vs NHE).     

Self-assembly of gold(I) rings and reversible formation of organometallic [2]catenanes

The reaction of the digold(I) diacetylide [(AuCCCH2OC6H4)2CMe2] with diphosphane ligands can lead to formation of either macrocyclic ring complexes or [2]catenanes by self-assembly. This gives an easy route to rare organometallic [2]catenanes, and the effect of the diphosphane ligand on the selectivity of self-assembly is studied. With diphosphane ligands Ph2P(CH2)xPPh2, the simple ring complex [Au2[(CCCH2OC6H4)2CMe2](Ph2P(CH2)xPPh2)] is formed selectively when x = 2, but the [2]catenanes [Au2[(CCCH2OC6H4)2CMe2](Ph2P(CH2)xPPh2)]2 are formed when x = 4 or 5. When x = 3, a mixture of the simple ring and [2]catenane is formed, along with the "double-ring" complex, [Au4[(CCCH2OC6H4)2CMe2]2(Ph2P(CH2)3PPh2)2] and a "hexamer" Au2[(CCCH2OC6H4)2CMe2](Ph2P(CH2)3PPh2)]6] whose structure is not determined. A study of the equilibria between these complexes by solution NMR techniques gives insight into the energetics and mechanism of [2]catenane formation. When the oligomer [(AuCCCH2OC6H4)2CMe2] was treated with a mixture of two diphosphane ligands, or when two [2]catenane complexes [[Au2[(CCCH2OC6H4)2CMe2](diphosphane)]2] were allowed to equilibrate, only the symmetrical [2]catenanes were formed. The diphosphanes Ph2PCCPPh2, trans-[Ph2PCH=CHPPh2] and (Ph2PC5H4)2Fe give the corresponding ring complexes [Au2[(CCCH2OC6H4)2CMe2](diphosphane)], and the chiral, unsymmetrical diacetylide [Au2[(CCCH2OC6H4C(Me)(CH2CMe2)C6H3OCH2CC)] gives macrocyclic ring complexes with all diphosphane ligands Ph2P(CH2)xPPh2 (x = 2-5).     

Chloromethylation of substituted di(2-thienyl)methanes and the reductive desulfuration of some diamines of the thiopene series

The action of chloromethyl ether on di(2-thienyl)methane, 1, 1-di-(2-thienyl)ethane, 2, 2-di(2-thienyl)propane, 2, 5-bis(dimethyl-2-thienylmethyl)thiophene, and 1, 1, 1-tri(2-thienyl)ethane has given, respectively: 5-chloromethyl -2 -thienylthiophene, 1, 1-bis(5-chloro-methyl-2-thienyl)ethane, 2, 2-bis(5-chloromethyl-2-thienyl)propane, 2, 5-bis(dimethyl-5-chloromethyl-2-thienylmethyl)thiophene, 1-(2-thienyl)-1, 1-bis(5-chloromethyl-2-thienyl)-ethane, and the corresponding amines: 5-diethylaminomethyl-2-thienylthiophene, 1,1-Bis(5-diethylaminomethyl-2-thienyl)ethane, 2, 2-bis(5-aminomethyl-2 -thienyl)propane, 2, 2-bis(5-methylaminomethyl-2-thienyl)propane, 2, 5-bis(dimethyl-5-dimethylaminomethyl-2-thienylmethyl)thiophene, and 2, 8, 8, 14, 20, 20-hexamethyl-2, 14-diaza-3, 2, 3, 2-α-cyclotetrathiene. The reductive desulfonation over Raney nickel of the diacetyl derivatives of 2, 2-bis(5-aminomethyl-2-thienyl)propane and 2, 2-bis(5-methylaminomethyl-2-thienyl)propane has given the diacetyl derivatives of aliphatic amines.     

Chloromethylation of substituted di(2-thienyl)methanes and the reductive desulfuration of some diamines of the thiopene series

The action of chloromethyl ether on di(2-thienyl)methane, 1, 1-di-(2-thienyl)ethane, 2, 2-di(2-thienyl)propane, 2, 5-bis(dimethyl-2-thienylmethyl)thiophene, and 1, 1, 1-tri(2-thienyl)ethane has given, respectively: 5-chloromethyl -2 -thienylthiophene, 1, 1-bis(5-chloro-methyl-2-thienyl)ethane, 2, 2-bis(5-chloromethyl-2-thienyl)propane, 2, 5-bis(dimethyl-5-chloromethyl-2-thienylmethyl)thiophene, 1-(2-thienyl)-1, 1-bis(5-chloromethyl-2-thienyl)-ethane, and the corresponding amines: 5-diethylaminomethyl-2-thienylthiophene, 1,1-Bis(5-diethylaminomethyl-2-thienyl)ethane, 2, 2-bis(5-aminomethyl-2 -thienyl)propane, 2, 2-bis(5-methylaminomethyl-2-thienyl)propane, 2, 5-bis(dimethyl-5-dimethylaminomethyl-2-thienylmethyl)thiophene, and 2, 8, 8, 14, 20, 20-hexamethyl-2, 14-diaza-3, 2, 3, 2--cyclotetrathiene. The reductive desulfonation over Raney nickel of the diacetyl derivatives of 2, 2-bis(5-aminomethyl-2-thienyl)propane and 2, 2-bis(5-methylaminomethyl-2-thienyl)propane has given the diacetyl derivatives of aliphatic amines.     

A new family of mixed-valence dinuclear rhodium complexes containing the two metal centers in different stereochemical environments

A series of dinuclear chelate complexes of the general composition [Rh2(kappa2-L)2(mu-CR2)2(mu-SbiPr3)] (R = Ph, p-Tol; L = CF3CO2-, acac-, acac-f3-) and [Rh2Cl(kappa2-L)(mu-CR2)2(mu-SbiPr3)] (R = Ph, p-Tol; L = acac-, acac-f3-) has been prepared by replacement of the chloro ligands in the precursors [Rh2Cl2(mu-CR2)2(mu-SbiPr3)] by anionic chelates. The lability of the SbiPr3 bridge in the rhodium dimers is illustrated by the reactions of [Rh2(kappa2-acac)2(mu-CR2)2(mu-SbiPr3)] (7, 8) with Lewis bases such as CO, CNtBu, and SbEt3 which lead to the formation of the substitution products [Rh2(kappa2-acac)2(mu-CR2)2(mu-L')] (13-16) in excellent yields. Treatment of 7 and 8 with sterically demanding tertiary phosphanes PR3 (R3 = iPr3, iPr2Ph, iPrPh2, Ph3) affords the mixed-valence Rh0-RhII complexes [(kappa2-acac)2Rh(mu-CPh2)2Rh(PR3)] (21-24) and [(kappa2-acac)2Rh(mu-C(p-Tol)2]2Rh(PiPr3)] (25) for which there is no precedence. The terminal PiPr3 ligand of 21 is easily displaced by alkynes, CNtBu, and CO to give, by preserving the [(kappa2-acac)2Rh(mu-CPh2)2Rh] molecular core, the related dinuclear compounds 26-31 in which the coordination number of the Rh0 center is 3, 4, or 5. The molecular structures of [Rh2Cl(kappa2-acac)(mu-CPh2)2(mu-SbiPr3)] (5), [Rh2(kappa2-acac)2(mu-CPh2)2(mu-CO)] (13), [(kappa2-acac)2Rh(mu-CPh2)2Rh(PiPr3)] (21), and [(kappa2-acac)2Rh(mu-CPh2)2Rh(CNtBu)2] (30) have been determined crystallographically.     

钾镁氯化物(硫酸盐)与脲、水体系的溶度研究

报导了KCl-MgCl2-CO(NH2)2-H2O和K2SO4-MgSO4-CO（NH2）2-H2O两个四元体系在25℃时的溶度及其饱和溶液的折光率、密度，相应的溶度图和组成-折光率、组成-密度图．前一体系中形成3个三元化合物：MgCl2·4CO（NH2）2·2H2O、MgCl2·CO（NH2）2·4H2O和KCl·MgCl2·6H2O溶度盐份图由9支共饱线、4个四元无变点组成．四元体系的水量图、性质-组成图有类似的变化．后一体系中有2个异成份溶解化合物MgSO4·CO（NH2）2·2H2O和K2SO4·MgSO4·6H2O形成，溶度等温图由7支双饱溶度线、3个四元无变点组成．对两个体系相图的相似性和差异点进行了讨论．     

Gallane complexes with amido-amine ligands

Gallane complexes bearing amido-amine ligands -N(R)CH2CMe2CH2NMe2 [R = H or SiMe3 (TMS)], (H2Ga[N(H)CH2CMe2CH2NMe2])2, 1, H2Ga[N(TMS)CH2CMe2CH2NMe2], 2, (H(Cl)Ga[N(H)CH2CMe2CH2NMe2])2, 3, ([(TMS)2N](H)Ga[N(H)CH2CMe2CH2NMe2])2, 4, and HGa[N(TMS)CH2CMe2CH2NMe2]2, 5, were synthesized from the reactions of the quinuclidine adducts of mono- and dichlorogallane with the corresponding lithium amides. Structural determinations of compounds 1, 3, and 4 showed all were dimeric with bridging amido groups. Rather than bond to gallium the tertiary amine groups in 1 and 4 were hydrogen-bonded to the amino N-H. In the structure of compound 3 the amine group occupied an axial position in the trigonal bipyramidal geometry of the five-coordinate gallium. The results were rationalized in terms of the steric and electronic properties of gallium ligands.     

Synthesis of New Macrocyclic Schiff Bases Containing Pyrazole and Triazole as Subcyclic Units

The novel macrocyclic Schiff bases upon which were fused triazole and pyrazole units and containing N, O and S inside the macrocyclic ring as donor atoms were synthesized by condensation of appropriate bis(4‐amino‐1,2,4‐triazole‐3‐yl‐sulfanyl)alkanes 2a , 2b , 2c , 2d , 2e , 2f , 2g , 2h , 2i , 2j , 2k , 2l , 2m , 2n , 2o , 2p , 2q , 2r and pyrazoledialdehyde 3 in refluxing glacial acetic acid. The structural identities of these compounds were confirmed on the basis of spectrum.     

Film growth precursor development for metal nitrides. Synthesis, structure, and volatility of molybdenum(VI) and tungsten(VI) complexes containing bis(imido)metal fragments and various nitrogen donor ligands

The molybdenum and tungsten complexes W2(NtBu)4(pz)4(pzH).(C6H14)0.5 (pz = pyrazolate), M(NtBu)2(Me2pz)2(Me2pzH)2 (Me2pz = 3,5-dimethylpyrazolate), M(NtBu)2(tBu2pz)2 (tBu2pz = 3,5-di-tert-butylpyrazolate), M2(NtBu)4(Me2pz)2Cl2, W(NtBu)2(C2N3(iPr)2)2py2, M(NtBu)2-(CN4CF3)2py2, and W(NtBu)2(PhNNNPh)2 were prepared by various synthetic routes from the starting materials Mo(NtBu)2Cl2, W(NtBu)2(NHtBu)2, and W(NtBu)2Cl2py2. These new complexes were characterized by spectral and analytical methods and by X-ray crystal structure determinations. The volatilities and thermal stabilities were evaluated to determine the potential of the new complexes for use in thin film growth of metal nitride films. Mo(NtBu)2(tBu2pz)2 and W(NtBu)2(tBu2pz)2 were found to have the optimum combination of volatility and thermal stability for application in atomic layer deposition thin film growth procedures.     

Dinitrogen functionalization with terminal alkynes, amines, and hydrazines promoted by [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2): observation of side-on and end-on diazenido complexes in the reduction of N2 to hydrazine

Functionalization of the N2 ligand in the side-on bound dinitrogen complex, [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2), has been accomplished by addition of terminal alkynes to furnish acetylide zirconocene diazenido complexes, [(eta5-C5Me4H)2Zr(C[triple bond]CR)]2(mu2,eta2,eta2-N2H2) (R = nBu, tBu, Ph). Characterization of [(eta5-C5Me4H)2Zr(C[triple bond]CCMe3)]2(mu2,eta2,eta2-N2H2) by X-ray diffraction revealed a side-on bound diazenido ligand in the solid state, while variable-temperature 1H and 15N NMR studies established rapid interconversion between eta1,eta1 and eta2,eta2 hapticity of the [N2H2]2- ligand in solution. Synthesis of alkyl, halide, and triflato zirconocene diazenido complexes, [(eta5-C5Me4H)2ZrX]2(mu2,eta1,eta1-N2H2) (X = Cl, I, OTf, CH2Ph, CH2SiMe3), afforded eta1,eta1 coordination of the [N2H2]2- fragment both in the solid state and in solution, demonstrating that sterically demanding, in some cases pi-donating, ligands can overcome the electronically preferred side-on bonding mode. Unlike [(eta5-C5Me4H)2ZrH]2(mu2,eta2,eta2-N2H2), the acetylide and alkyl zirconocene diazenido complexes are thermally robust, resisting alpha-migration and N2 cleavage up to temperatures of 115 degrees C. Dinitrogen functionalization with [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) was also accomplished by addition of proton donors. Weak Br?nsted acids such as water and ethanol yield hydrazine and (eta5-C5Me4H)2Zr(OH)2 and (eta5-C5Me4H)2Zr(OEt)2, respectively. Treatment of [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) with HNMe2 or H2NNMe2 furnished amido or hydrazido zirconocene diazenido complexes that ultimately produce hydrazine upon protonation with ethanol. These results contrast previous observations with [(eta5-C5Me5)2Zr(eta1-N2)]2(mu2,eta1,eta1-N2) where loss of free dinitrogen is observed upon treatment with weak acids. These studies highlight the importance of cyclopentadienyl substituents on transformations involving coordinated dinitrogen.     

Multimetallic assemblies using piperazine-based dithiocarbamate building blocks

Treatment of cis-[RuCl2(dppm)2] (dppm = bis(diphenylphosphino)methane) with dithiocarbamates, NaS2CNR2 (R = Me, Et) and [H2NC5H10][S2CNC5H10], yields cations [Ru(S2CNR2)2(dppm)2](+) and [Ru(S2CNC5H10)2(dppm)2](+), respectively. The zwitterions S2CNC4H8NHR (R = Me, Et) react with the same metal complex in the presence of base to yield [Ru(S2CNC4H8NR)(dppm)2](+). Piperazine or 2,6-dimethylpiperazine reacts with carbon disulfide to give the zwitterionic dithiocarbamate salts H2NC4H6(R2-3,5)NCS2 (R = H; R = Me), which form the complexes [Ru(S2CNC4H6(R2-3,5)NH2)(dppm)2](2+) on reaction with cis-[RuCl2(dppm)2]. Sequential treatment of [Ru(S2CNC4H8NH2)(dppm)2](2+) with triethylamine and carbon disulfide forms the versatile metalla-dithiocarbamate complex [Ru(S2CNC4H8NCS2)(dppm)2] which reacts readily with cis-[RuCl2(dppm)2] to yield [{Ru(dppm)2}2(S2CNC4H8NCS2)]. Reaction of [Ru(S2CNC4H8NCS2)(dppm)2] with [Os(CH=CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole), [Pd(C6H4CH2NMe2)Cl]2, [PtCl2(PEt3)2], and [NiCl2(dppp)] (dppp = 1,3-bis(diphenylphosphino)propane) results in the heterobimetallic complexes [(dppm)2Ru(S2CNC4H8NCS2)ML(n))](m+) (ML(n) = Os(CH=CHC6H4Me-4)(CO)(PPh3)2](+), m = 1; ML(n) = Pd(C,N-C6H4CH2NMe2), m = 1; ML(n) = Pt(PEt3)2, m = 2; ML(n) = Ni(dppp), m = 2). Reaction of [NiCl2(dppp)] with H2NC4H8NCS2 yields the structurally characterized compound, [Ni(S2CNC4H8NH2)(dppp)](2+), which reacts with base, CS2, and cis-[RuCl2(dppm)2] to provide an alternative route to [(dppm)2Ru(S2CNC4H8NCS2)Ni(dppp)](+). A further metalla-dithiocarbamate based on cobalt, [CpCo(S2CNC4H8NH2)(PPh3)](2+), is formed by treatment of CpCoI2(CO) with S2CNC4H8NH2 followed by PPh3. Further reaction with NEt3, CS2, and cis-[RuCl2(dppm)2] yields [(Ph3P)CpCo(S2CNC4H8NCS2)Ru(dppm)2](2+). Heterotrimetallic species of the form [{(dppm)2Ru(S2CNC4H8NCS2)}2M](2+) result from the reaction of [Ru(S2CNC4H8NCS2)(dppm)2] and M(OAc)2 (where M = Ni, Cu, Zn). Reaction of [Ru(S2CNC4H8NCS2)(dppm)2] with Co(acac)3 and LaCl3 results in the formation of the compounds [{(dppm)2Ru(S2CNC4H8NCS2)}3Co](3+) and [{(dppm)2Ru(S2CNC4H8NCS2)}3La](3+), respectively. The electrochemical behavior of selected examples is also reported.     

Synthesis and characterization of well-defined aluminum-containing heterobimetallic selenides

A series of novel aluminum heterobimetallic selenides were reported. The reaction of LAl(SeH)2 (1) with LiN(SiMe3)2 resulted in the formation of [LAl(SeLi)2(THF)2] (2) (L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3). Compound 2 reacted with Me2GeCl2, Ph2GeCl2, Cp2TiCl2, and Cp2ZrCl2, respectively, to produce LAl(mu-Se)2GeMe2 (3), LAl(mu-Se)2GePh2 (4), LAl(mu-Se)2TiCp2 (5), and LAl(mu-Se)2ZrCp2 (6) in moderate yields. Compounds 2-6 were characterized by elemental analysis, NMR, and electron impact-MS. The X-ray single-crystal structure of 3 is reported and confirms the spirocyclic arrangement of the aluminum atom within the six-membered AlN2C3 and four-membered AlSe2Ge rings.     

Derivatives of unsaturated phosphonic acids

Summary The following compounds were synthesized by the reaction of secondary aliphatic amines with 2-alkoxyl-and 2 phenoxy vinylphosphonic dichlorides: the bisdimethylamides of 2-ethoxy-, 2-isopropoxy-, 2-butoxy, and 2 phonoxy vinylphosphonic acids; teh bisdiethylamides of 2-ethoxy-, 2-isopropoxy-, 2-butoxy-, and 2-phenoxyvinylphosphonic acids; the bisdibutylamides of 2-ethoxy-, 2-propoxy-, 2-isopentyloxy-, and 2-phenoxyl-vinyl-phosphonic acids; and the dipiperidides of 2-ethoxy-, 2-butoxy-, and 2-phenoxyl-vinylphosphonic acids.     

Toward a magnetostructural correlation for a family of Mn6 SMMs

We have structurally and magnetically characterized a total of 12 complexes based on the Single-Molecule Magnet (SMM) [MnIII6O2(sao)6(O2CH)2(MeOH) 4] (1) (where sao2- is the dianion of salicylaldoxime or 2-hydroxybenzaldeyhyde oxime) that display analogous structural cores but remarkably different magnetic behaviors. Via the use of derivatized oxime ligands and bulky carboxylates we show that it is possible to deliberately increase the value of the spin ground state of the complexes [Mn6O2(Me-sao)6(O2CCPh3)2(EtOH)4] (2), [Mn6O2(Et-sao)6(O2CCMe3)2(EtOH)5] (3), [Mn6O2(Et-sao)6(O2CPh2OPh)2(EtOH)4] (4), [Mn6O2(Et-sao)6(O2CPh4OPh)2(EtOH)4(H2O)2] (5), [Mn6O2(Me-sao)6(O2CPhBr)2(EtOH)6] (6), [Mn6O2(Et-sao)6(O2CPh)2(EtOH)4(H2O)2] (7), [Mn6O2(Et-sao)6{O2CPh(Me)2}2(EtOH)6] (8), [Mn6O2(Et-sao)6(O2C11H15)2(EtOH)6] (9), [Mn6O2(Me-sao)6(O2C-th)2(EtOH)4(H2O)2] (10), [Mn6O2(Et-sao)6(O2CPhMe)2(EtOH)4(H2O)2] (11), and [Mn6O2(Et-sao)6(O2C12H17)2(EtOH)4(H2O)2] (12) (Et-saoH2 = 2-hydroxypropiophenone oxime, Me-saoH2 = 2-hydroxyethanone oxime, HO2CCPh3 = triphenylacetic acid, HO2CCMe3 = pivalic acid, HO2CPh2OPh = 2-phenoxybenzoic acid, HO2CPh4OPh = 4-phenoxybenzoic acid, HO2CPhBr = 4-bromobenzoic acid, HO2CPh(Me)2 = 3,5-dimethylbenzoic acid, HO2C11H15 = adamantane carboxylic acid, HO2C-th = 3-thiophene carboxylic acid, HO2CPhMe = 4-methylbenzoic acid, and HO2C12H17 = adamantane acetic acid) in a stepwise fashion from S = 4 to S = 12 and, in-so-doing, enhance the energy barrier for magnetization reorientation to record levels. The change from antiferromagnetic to ferromagnetic exchange stems from the "twisting" or "puckering" of the (-Mn-N-O-)3 ring, as evidenced by the changes in the Mn-N-O-Mn torsion angles.     

f-Element disiloxanediolates: novel Si-O-based inorganic heterocycles

The preparation and structural characterization of scandium and f-element complexes derived from the disiloxanediolate dianion, [(Ph2SiO)2O]2-, are reported. Reactions of in situ prepared Ln[N(SiMe3)2]3 (Ln = Eu, Sm, Gd) with (Ph2SiOH)2O in different stoichiometries afforded the lanthanide disiloxanediolates [Eu[[(Ph2SiO)2O]Li(Et2O)]3] (1), [[[(Ph2SiO)2O]Li(dme)]2SmCl(dme)] (2), and [[[((Ph2SiO)2O]Li(thf)2]2GdN(SiMe3)2] (3). In situ formed (Ph2SiOLi)2O reacted with anhydrous NdBr3 (molar ratio 3:1) to give polymeric [[Nd[(Ph2SiO)2O]3[mu-Li(thf)]2[mu2LiBrLi(thf)(Et2O)]]n] (4). Treatment of 3 with Ph2Si(OH)2 in the presence of acetonitrile yielded the dilithium trisiloxanediolate derivative [[Ph2Si(OSiPh2O)2][Li(MeCN)]2]2 (5), which according to an X-ray analysis displays an Li4O4 heterocubane structure. The trinuclear scandium complex [[[(Ph2SiO)2O]Sc(acac)2]2Sc(acac)] (6) was obtained by reaction of [(C5Me5)Sc(acac)2] (C5Me5 = eta5-pentamethylcyclopentadienyl) with (Ph2SiOH)2O in a 3:2 molar ratio. Selective formation of the colorless uranium(VI) derivative [U[Ph2Si(OSiPh20)2]2[(Ph2SiO)2O]] (7) was observed when uranocene, U(eta8-C8H8)2, was allowed to react with (Ph2SiOH)2O. An X-ray diffraction study of the solvated derivative [U[Ph2Si(OSiPh2O)2]2[(Ph2SiO)2O]].Et2O.TMEDA (TMEDA= N,N,N',N'-tetramethyl-ethylenediamine) (7a) revealed the presence of both the original [(Ph2SiO)2O]2- dianion as well as the ring-enlarged [Ph2Si(OSiPh2O)2]2- ligand in the same molecule.     

Regioselective and reversible carbon-nitrogen bond formation: synthesis, structure and reactivity of ureato-bridged complexes [Mo2(NAr)2(mu-X){mu-ArNC(O)NAr}(S2CNR2)2](Ar = Ph, p-tol; X = S, NAr; R = Me, Et, Pr)

Reaction of ArNCO with syn-[MoO(mu-O)(S2CNR2)]2 or syn-[MoO(mu-NAr)(S2CNR2)]2 at 110 degrees C leads to the facile formation of bridging ureato complexes [Mo2(NAr)2(mu-NAr){mu-ArNC(O)NAr}(S2CNR2)2](Ar = Ph, p-tol; R = Me, Et, Pr), formed upon substitution of all oxo ligands and addition of a further equivalent of isocyanate across one of the bridging imido ligands. Related sulfido-bridged complexes [Mo2(NAr)2(mu-S){mu-ArNC(O)NAr}(S2CNR2)2] have been prepared from syn-[Mo2O2(mu-O)(mu-S)(S2CNR2)2]. When reactions with syn-[MoO(mu-NAr)(S2CNEt2)]2 were followed by NMR, intermediates were observed, being formulated as [Mo2O(NAr)(mu-NAr){mu-ArNC(O)NAr}(S2CNEt2)2], which at higher temperatures convert to the fully substituted products. A crystallographic study of [Mo2(N-p-tol)2(mu-S){mu-p-tolNC(O)N-p-tol}(S2CNPr2)2] reveals that the bridging ureato ligand is bound asymmetrically to the dimolybdenum centre-molybdenum-nitrogen bonds trans to the terminal imido ligands being significantly elongated with respect to those cis-a result of the trans-influence of the terminal imido ligands. This trans-influence also leads to a trans-effect, whereby the exchange of aryl isocyanates can occur in a regioselective manner. This is followed by NMR studies and confirmed by a crystallographic study of [Mo2(N-p-tol)2(mu-N-p-tol){mu-p-tolNC(O)NPh}(S2CNEt2)2]--the PhNCO occupying the site trans to the terminal imido ligands. Ureato complexes also react with PhNCS, initially forming [Mo2(NAr)2(mu-S){mu-ArNC(O)NAr}(S2CNR2)2], resulting from exchange of the bridging imido ligand for sulfur, together with small amounts of [Mo2(NAr)2(mu-S)(mu-S2)(S2CNEt2)2], containing bridging sulfide and disulfide ligands. The ureato complexes [Mo2(NAr)2(mu-S){mu-ArNC(O)NAr}(S2CNR2)2] react further with PhNCS to give [Mo2(NAr)2(mu-S)2(S2CNR2)2]n (n = 1, 2), which exist in a dimer-tetramer equilibrium. In order to confirm these results crystallographic studies have been carried out on [Mo2(N-p-tol)2(mu-S)(mu-S2)(S2CNEt2)2] and [Mo2(N-p-tol)2(mu-S)2(S2CNPr2)2]2.     

Phosphine-substituted dithiolene complexes as ligands: communication between ruthenium(II) centers through a dimolybdenum bis(dithiolene) core

The reaction of Mo2(SCH2CH2S)2Cp2 (1; Cp=eta-C5H5) with an excess of an alkyne in refluxing dichloromethane affords the bis(dithiolene) complexes Mo2(micro-SCR1=CR2S)2Cp2 (2a, R1=R2=CO2Me; 2b, R1=R2=Ph; 2c, R1=H, R2=CO2Me) whereas with 1 equiv of alkyne at room temperature the mixed dithiolene-dithiolate species Mo2(micro-SCR1=CR2S)(micro-SCH2CH2S)Cp2 (3a, R1=R2=CO2Me; 3b, R1=R2=Ph) are formed. The remaining dithiolate ligand in 3 can then be converted into a different dithiolene by reaction with a second alkyne. Applying this methodology, we have used bis(diphenylphosphino)acetylene to prepare the first examples of complexes containing phosphine-substituted dithiolene ligands: Mo2{micro-SC(CO2Me)=C(CO2Me)S}{micro-SC(PPh2)=C(PPh2)S}Cp2 (2g) and Mo2{micro-SC(PPh2)=C(PPh2)S}2Cp2 (2h). Tri- and tetrametallic complexes can then be assembled by coordination of these diphosphines to CpRuCl units by reaction with CpRu(PPh3)2Cl. Electrochemical studies of the Ru(II)/Ru(III) couple in Mo2{micro-SC(PPh2)=C(PPh2)S}2Cp2(RuClCp)2 (4b) reveals that the two separate ruthenium centers are oxidized electrochemically at different potentials, demonstrating communication between them through the dimolybdenum bis(dithiolene) core. Density functional theory calculations were carried out to explore the electronic structures of these species and to predict and assign their electronic spectra.     

When arsine makes the difference: chelating phosphino and bridging arsinoarylthiolato gallium complexes

The (organo)gallium compounds GaCl{(SC6H4-2-PPh2)-kappa2S,P}2 (1), Ga{(SC6H4-2-PPh2)-kappa2S,P}{(SC6H4-2-PPh2)-kappaS}2 (2), GaMe2{(SC6H4-2-PPh2)-kappa2S,P} (3), GatBu2{(SC6H4-2-PPh2)-kappa2S,P} (4), GatBu{(SC6H4-2-PPh2)-kappa2S,P}{(SC6H4-2-PPh2)-kappaS} (5), [GaMe2{(mu2-SC6H4-2-AsPh2)-kappaS}]2 (6), and GatBu{(SC6H4-2-AsPh2)-kappa2S,As}{(SC6H4-2-AsPh2)-kappaS} (7) were obtained from the reaction of 2-EPh2C6H4SH (E = P (PSH), As (AsSH)) with GaCl3 (1, 2) or GaR3 (R = Me, tBu; 3-7) in different molar ratios and under different reaction conditions. Compound 2 was also obtained from Li(PS) and GaCl3 (3.5:1). While a monomeric structure with a chelating phosphinoarylthiolato ligand is observed in GaMe2{(SC6H4-2-PPh2)-kappa2S,P} (3), a dimeric arsinoarylthiolato-bridged complex [GaMe2{(mu2-SC6H4-2-AsPh2)-kappaS}]2 (6) is obtained with the corresponding AsS- ligand. B3LYP/6-31G(d) calculations show that although the dimer is thermodynamically favored for both ligands, the formation of 3 is due to the combination of higher stability of the chelate compared with the monodentate phosphorus ligand and a higher barrier for the ring opening of the PS- than of the AsS- chelate.