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Reaction of Pd(2)(DAniF)(4), 1, (DAniF = di-p-anisylformamidinate) with 1 equiv of AgPF(6) in CH(2)Cl(2) at or below -10 degrees C produces the paramagnetic species [Pd(2)(DAniF)4]PF(6), 1-PF(6), that has been studied by X-ray crystallography, UV-vis spectroscopy, electrochemistry, and multifrequency (9.5, 34.5, 110, and 220 GHz) EPR spectroscopy. Upon oxidation of the precursor, the Pd-Pd distance decreases by 0.052 Angstrom from 2.6486(8) to 2.597(1) Angstrom. The EPR spectra show broad signals with line widths of about 1000 G. The spectra collected at high field show a large spread of g tensor components ( approximately 0.03), but these are masked at lower frequencies (9.5 and 34.5 GHz). A reinvestigation using high-field EPR of the p-tolyl analogue, which is the only other structurally characterized Pd(2)(5+) species (Cotton, F. A.; Matusz, M.; Poli, R.; Feng, X. J. Am. Chem. Soc. 1988, 110, 1144), shows that this species, which had been reported to give an isotropic 9.5 GHz EPR spectrum, also gives anisotropic 110 and 220 GHz EPR spectra with a similarly large spread of g tensor components consistent with the unpaired electron residing in a metal-based MO. The results of these studies and calculations using density functional theory are consistent with the oxidation being metal-based, resulting in an uncommon Pd(2)(5+) species with a Pd-Pd bond order of 1/2.

Compounds of nickel in which a chain of three metal atoms is closely embraced by two interlocking heptadentate dianions derived from a chain of five pyridyl groups linked at the 2, or 2 and 6, positions by four amide nitrogen atoms are reported. This new type of extended metal atom chain (EMAC) compound differs from earlier ones in that ligand exchange at the axial positions cannot occur, because the axial ligands are part of the entire ligand. Four such compounds, all crystallographically characterized, are reported. This work is a proof-of-concept project that will be extended to other metals with these and other homologous ligands.

Two molecular pairs [Mo2(DAniF)3]2[N,N'-diethylterephthalamidate] (1) and [Mo2(DAniF)3]2{1,3-C6H4[C(O)NP]} (2) where DAniF = N,N'-di-p-anisylformamidinate) and the propeller ([Mo2(DAniF)3]3{1,3,5-C6H3[C(O)NPh]3} (3)) have been prepared in good yield and high purity by directly combining Mo2(DAniF)3(O2CCH3) with the corresponding polyamidates. Electrochemical measurements of these complexes show unresolved redox waves, which indicate that the dimetal centers are only electronically weakly coupled. Compound 1 was chemically oxidized by ferrocenium tetrafluoroborate to the two-electron oxidation product 4, where one electron was removed from each of the [Mo2] units. The hyperfine coupling in the EPR spectrum (A = 22 x 10-4 cm-1 ) suggests that 4 is an electron-trapped species with one electron residing on each of the two dimolybdenum units, as suggested also by electrochemical measurements.

Reactions of [cis-Mo2(DAniF)2(NCCH3)4](BF4)2, DAniF = N,N'-di-p-anisylformamidinate, with an excess of anhydrous Bu(n)4NX (X = Cl, Br, I), produced the halide-bridged tetranuclear clusters, [cis-Mo2(DAniF)2]2(mu-X)4, X = Cl (1), Br (2), and I (3). All three compounds show two reversible one-electron oxidation processes with potential separations (DeltaE(1/2)) between the two oxidation processes of 540, 499, and 440 mV, respectively. These DeltaE(1/2) values show that the strength of the electronic coupling between the dimetal units decreases as the Mo2...Mo2 distance increases from 1 to 2, and then to 3. The structures, EPR spectra, and near-IR (NIR) spectra of the corresponding mixed-valence species (1-PF6, 2-PF6, and 3-PF6) indicate that the clusters are electronically delocalized. Calculations at the DFT level indicate that the strong electronic communication is principally due to a direct overlap between the delta orbitals from the adjacent dimetal units.

A pair of isomeric cyclic triads containing three quadruply bonded [Mo2] units, [Mo2(cis-DAniF)2]2+ (DAniF = N,N'-di-p-anisylformamidinate), bridged by six fluoride anions, has been synthesized and crystallographically characterized. For the alpha isomer, the three [Mo2] units are oriented in two orthogonal directions. Two of them are structurally equivalent and parallel to each other, but oriented perpendicular to the third one. The beta isomer is a triangle with three geometrically identical [Mo2] units, parallel to each other, as the vertices. Thus, the beta isomer possesses idealized D3h symmetry while the alpha isomer only has C2v symmetry. These two isomers do not interconvert in boiling THF or toluene or under irradiation with ultraviolet light, but oxidation of the alpha isomer first generates an alpha+ species that changes to beta+. The two isomers have very similar electrochemical behavior, both showing three reversible one-electron redox processes for the [Mo2] centers and similar potential separations (DeltaE(1/2)). The first and second redox couples are well separated (ca. 390-410 mV), while the second and third ones are separated by only about 150 mV.

A series of tetranuclear compounds consisting of two {Mo2[(m-CF3C6H4)NC(H)N(m-CF3C6H4)]3}n+ moieties linked by two OH- or two O2- ions has been characterized. Abbreviating the dimolybdenum plus three spectator bridging ligands as [Mo2], the following three compounds have been made-[Mo2](mu-OH)2[Mo2] (1), [Mo2](mu-O)2[Mo2] (2), and {[Mo2](mu-O)2[Mo2]}SbF6 (3). Compound 1, which is diamagnetic and contains quadruply bonded Mo2(4+) units, is converted to diamagnetic 2 by oxidation with O2. Compound 2, which has Mo2(5+) units, is oxidized by NOSbF6 to 3 which has a rare Mo2(5.5+) core and an odd electron delocalized over the two dimolybdenum units.

A general method for the syntheses of dipalladium compounds having a singly bonded Pd26+ core and the formula R,S-cis-Pd2(C6H4PPh2)2(O2CR)2Cl2 is described. When the alkyl group in the carboxylate ligands is an electron donating group, the compounds are stable and the yields high. The Pd-Pd distances for the diamagnetic compounds with R = CF3 and CMe3 are 2.5434(4) and 2.5241(9) A, respectively. Calculations at the DFT level suggest that the electronic configuration is sigma2pi4delta2delta*2pi*4. These represent rare examples of palladium(III) compounds.

The syntheses of two analogues of the bicyclic guanidinate ligand hpp (hpp = the anion of the guanidine-type compound 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2a]pyrimidine) which contain two fused rings are reported. Each compound contains one seven-membered ring while the other is either a five (Htbd) or a six (Htbu) membered ring. In THF/Bu4NPF6, the dimolybdenum compounds Mo2(tbd)4 and Mo2(tbu)4 are easily oxidized and they have signals in the differential pulse voltammograms at -1.059 and -1.009 V (vs. Ag/AgCl), respectively and for the Mo2(5+/6+) couples and in the same order -0.242 and -0.312 V for the Mo2(6+/5+) couples. The two compounds produce the corresponding Mo2(bicyclic guanidinate)4Cl compounds immediately upon dissolution in CH2Cl2 and these easily form species with Mo2(6+) cores. In Mo2(tbd)4Cl there are two crystallographically independent molecules with Mo-Mo distances of 2.1711(7) and 2.1690(7) A. The distance between metal atoms increases to 2.206(1) A upon oxidation to Mo2(tbd)4Cl2 which has a triply bonded Mo2(6+) core. For the diamagnetic compound Mo2(tbu)4 this distance is 2.0677(9) A and it increases to 2.133(2) A upon reduction of the bond order from 4 to 3.5 in the paramagnetic compound Mo2(tbu)4Cl.

A series of five bicyclic guanidinate compounds containing various combinations of five- and six-membered rings and substituted alkyl groups have been shown by photoelectron spectroscopy to be easily ionized, with the one having two six-membered rings and four ethyl groups being the most easily ionized. The corresponding anions are capable of forming paddlewheel compounds having quadruply bonded Mo2(4+) units which are also easy to ionize. The most easily ionized compound is the ethyl-substituted Mo2(TEhpp)4 complex which has a broad first ionization band centered around 4.27 +/- 0.03 eV and an ionization onset at the very low energy of 3.93 +/- 0.03 eV. Even the compound with ligands containing two five-membered rings, which favors a long Mo-Mo separation because of the large ligand bite, has an ionization energy (4.78 eV) that is less than those of well-known organometallic reducing agents such as (eta5-C9Me7)2Co and (eta5-C5Me5)2Cr.

A dynamic equilibrium has been found in CDCl3 between a neutral molecular square, [cis-Mo2(DAniF)2]4(O2CC6F4CO2)4 (1) and triangle, [cis-Mo2(DAniF)2]3(O2CC6F4CO2)3 (2) (DAniF = the anion of N,N'-di-p-anisylformamidine). The two components have been crystallographically characterized and solution studies by 1H and 19F NMR spectra of the concentration- and the temperature-dependence of the equilibrium have been performed. The conversion of three moles of molecular squares 1 to four moles of molecular triangles 2 has an equilibrium constant of 1.98(7) x 10(-4) at 23.7 degrees C. At this temperature, the DeltaG(0) for the conversion of three moles of squares to four moles of triangles is 21.0 kJ mol(-1). The conversion is enthalpically disfavored (DeltaH(0) = 23.5 kJ mol(-1)), but entropically favored (DeltaS(0) = 8.2 J K(-1) mol(-1)).

Tetranuclear Mo4 clusters with two quadruply bonded Mo2(4+) units, [Mo2(cis-DAniF)2] (DAniF = N,N'-di-p-anisylformamidinate), linked by alkoxides (OCH3 for 1 and OC2H5 for 4) have been prepared. The nonbonding separation between the midpoints of the quadruply bonded units, ca. 3.24 A, is the shortest among compounds having two linked Mo2(4+) units. Electrochemical measurements show two redox waves for each compound with large DeltaE(1/2) values (554 and 587 mV for 1 and 4, respectively) that correspond to K(C) values on the order of 10(9). The large electronic communication is attributed to the short separation between dinuclear units that favor direct delta-to-delta orbital interactions between the two dimetal centers. Compound 1 was chemically oxidized using stoichiometric amounts of ferrocenium salts to a one-electron oxidation product 2 (in which the counteranion is PF6-) and a two-electron oxidation product 3 (which contains two BF4- anions). Upon oxidation there are significant decreases in the distance between the two [Mo2] units to 3.100 A and then to 2.945 A. The mixed-valence species 2 shows two broad absorption bands at 5900 and 7900 cm(-1) in the NIR region which are assigned to the HOMO-1 --> SOMO and HOMO-2 --> SOMO transitions. Compound 3 is fluxional in solution, as shown by variable-temperature 1H NMR spectra. The sharp signals in the NMR spectrum at -50 degrees C and the lack of an EPR signal suggest that this species is diamagnetic and that a four-center, two-electron bond is formed in the cyclometallic Mo4 cluster. To a first-order approximation, an average bond order of 0.25 is assigned to the bonding interaction between the two Mo atoms along the long edges of the rectangle defined by the four Mo atoms.

Two bicyclic guanidinate ligands consisting of 5,5-membered (tbo) and 5,6-membered (tbn) rings have been used for the preparation of dimolybdenum compounds, such as Mo2(tbo)4 and Mo2(tbo)4Cl, and species containing Mo2(tbn)4(n+) with n = 0-2. The compounds with quadruply bonded Mo2(4+) species are strong reducing agents and have potentials of about -1 V (vs Ag/AgCl) for the Mo2(5+/4+) process. The structure of the THF solvate of Mo2(tbo)4 shows the longest Mo-Mo bond distance, 2.1453(4) A, for a quadruply bonded species, and this is due to a large divergent angle induced by the geometry of the ligand. This distance increases to 2.2305(8) A upon oxidation by CH2Cl2 to Mo2(tbo)4Cl. For the 5,6-membered-ring ligand tbn, even though the divergent angle is large compared to formamidinate ligands, it is not as large as that in tbo, and the Mo-Mo distance in Mo2(tbn)4, 2.082(1) A, is in the normal range for paddlewheel Mo2(4+) compounds. This distance increases to 2.2233(8) A upon oxidation by O2 in CH2Cl2, which forms Mo2(tbn)4Cl2 x CH2Cl2.

Dinickel(II) complexes of the ligands N,N'-di-p-anisylformamidinate (DAniF) and N,N',N''-triphenylguanidinate (TPG) have been synthesized and crystallographically characterized, along with their one-electron-oxidized analogues. In both systems, the Ni-Ni distances become shorter by approximately 0.1 A upon oxidation, in accord with the proposal that the resulting Ni2(5+) complexes are appropriately described as having one electron removed from a metal-based sigma orbital and an overall Ni-Ni bond order of 1/2. Although conventional DFT calculations on the model compounds Ni2(HNCHNH)4 and [Ni2(HNCHNH)4]+ appear to predict that the lowest energy state of the latter species would have one unpaired electron in an essentially ligand-based orbital. A single-point calculation of Ni2(DAniF)4 employing the geometry of its crystal structure with the full ligand included reveals a reversal of the previously predicted order of the HOMO and HOMO-1, and suggests that the unpaired electron in [Ni2(DAniF)4]+ is in a metal-based orbital of sigma symmetry. This is verified by the axial EPR spectrum of the compound in solution. The compound Ni2(DAniF)4 shows an unexpectedly rich cyclic voltammogram with four stepwise reversible oxidation waves. Coulometric experiments show that the doubly oxidized species has a significant lifetime at -25 degrees C, and by spectroelectrochemistry, its UV-vis spectrum was recorded. We propose that this species contains a Ni2(6+) core with a single Ni-Ni sigma bond.

Reaction of Ti[N(But)Ar]3 (Ar = 3,5-C6H3Me2 or Ar' = C6H5) with CO2 at -40 degrees C produces diamagmetic Ti(III) paddlewheel complexes with long Ti-Ti separations (>3.4 Angstrom), thus excluding direct Ti-Ti bonding. 1H NMR spectroscopy shows that the compounds are diamagnetic in solution in the temperature range of -65 to +70 degrees C. In the solid state, the diamagnetism was found to persist between 2 and 300 K. Calculations at the density functional theory level suggest that the diamagnetism results from antiferromagnetic coupling by superexchange through the ligand pi system.

The ground-state electronic structure of the trinuclear complex Cu3(dpa)4Cl2 (1), where dpa is the anion of di(2-pyridyl)amine, has been investigated within the framework of density functional theory (DFT) and compared with that obtained for other known M3(dpa)4Cl2 complexes (M = Cr, Co, Ni) and for the still hypothetical Ag3(dpa)4Cl2 compound. Both coinage metal compounds display three singly occupied x2-y2-like (delta) orbitals oriented toward the nitrogen environment of each metal atom, generating antibonding M-(N4) interactions. All other metal orbital combinations are doubly occupied, resulting in no delocalized metal-metal bonding. This is at variance with the other known symmetric M3(dpa)4Cl2 complexes of the first transition series, which all display some delocalized bonding through the metal backbone, with formal bond multiplicity decreasing in the order Cr > Co > Ni. An antiferromagnetic coupling develops between the singly occupied MOs via a superexchange mechanism involving the bridging dpa ligands. This magnetic interaction can be considered as an extension to the three aligned Cu(II) atoms of the well-documented exchange coupling observed in carboxylato-bridged dinuclear copper compounds. Broken-symmetry calculations with approximate spin projection adequately reproduce the coupling constant observed for 1. Oxidation of 1 removes an electron from the magnetic orbital located on the central Cu atom and its ligand environment; 1+ displays a much weaker antiferromagnetic interaction coupling the terminal Cu-N4 moieties via four ligand pathways converging through the x2-y2 orbital of the central metal. The silver homologues of 1 and 1+ display similar electronic ground states, but the calculated magnetic couplings are stronger by factors of about 3 and 4, respectively, resulting from a better overlap between the metal centers and their equatorial ligand environment within the magnetic orbitals.

By employing cis-Mo2(DAniF)2(2+) (DAniF = N,N'-di(p-anisyl)formamidinate) as the vertex building block and terephthaloyldiamidate as the linker, four dimolybdenum-containing cyclic oligomers have been synthesized and structurally characterized. In these compounds, described by the general formula [cis-Mo2(DAniF)2((ArNOC)2C6H4)2]n, n = 3 and 4, the geometry and composition of the products are affected by the identity of the aromatic groups of the linker. When Ar = phenyl, n = 3 (1a and 1b); however, n = 4 for Ar = p-trifluoromethylphenyl (2) and when Ar = m-trifluoromethylphenyl (3). All these compounds have a central cavity, shaped by the diamidate linker, that is capable of serving as host to guest molecules in a selective manner. For compounds 2 and 3, self-assembly that takes place in the crystalline state entails intermolecular C-H...F-C interactions. Such interactions generate a one-dimensional network with a tunnel cross section of 10 x 10 A(2) in 2, whereas in 3, they result in a cage in which two THF molecules are encapsulated. The F...H distances vary in a broad range from 2.38 to 2.70 A.

Unprecedented strong electronic communication has been found in dimolybdenum pairs containing quadruply bonded Mo2(DAniF)3(+) (DAniF = N,N'-di-p-anisylformamidinate) units linked by dioxolene (C6X2O4(2-)) anions. The neutral compounds [Mo2(DAniF)3]2(C6X2O4) (1, X = H; 2, X = Cl; 3, X = NO2) and the singly oxidized products {[Mo2(DAniF)3]2(C6X2O4)Mo2}PF6 (4, X = H; 5, X = Cl) have been synthesized and characterized by X-ray crystallography and spectroscopic methods. Unusually short Mo-O distances (approximately 2.05 A for 1 and 2, and approximately 2.01 A for 4 and 5) are implicated in the remarkably strong interaction between [Mo2] units via the linkers. This leads to an extensive charge delocalization in the mixed-valence species, which is mediated by the dioxolene linker, as revealed by the large deltaE(1/2) values (763, 795, and 816 mV for 1, 2, and 3, respectively). Additional evidence for the strong electronic coupling is provided by UV-vis, NIR, and EPR spectroscopies and DFT calculations.

Single-molecule transistors incorporating trimetal molecules of Cu(3)(dpa)(4)Cl(2) and Ni(3)(dpa)(4)Cl(2) (dpa = 2,2'-dipyridylamide) have been fabricated. Conductance is measured as a function of bias and gate voltages at low temperature, showing single-electron tunneling behavior through the molecules. Additional structures corresponding to the excitations in the molecules are observed, which can be attributed to intramolecular vibrational excitations coupled to the electron tunneling processes. The energies of the vibrational states are dependent on the redox state of the included molecules.

The large rigid dianion fluoflavinate, C(14)H(8)N(4)(2)(-), consisting of four fused and planar six-membered rings with four nitrogen donor atoms, has been used to link two metal-to-metal bonded and redox-active Mo(2)(n)()(+) units which are each locally bridged by three additional groups, collectively denoted [Mo(2)]. In 1, the [Mo(2)] units are Mo(2)(DAniF)(3) (DAniF = N,N'-di-p-anisylformamidinate), and in 5, they are trans-Mo(2)(DAniF)(2)(O(2)CCH(3)) groups. These [Mo(2)](fluoflavinate)[Mo(2)] compounds show three reversible one-electron oxidation steps, one more than all other [Mo(2)](linker)[Mo(2)] species known to date. The first two redox processes are metal-based, and the third one has been assigned to a ligand oxidation by comparison to that of paddlewheel compound 4 which contains only one dimolybdenum unit with a monoanionic fluoflavinate ligand. Chemical oxidations of 1 produce the singly- and doubly-oxidized species 2 and 3, respectively. All compounds have been characterized by X-ray crystallography and, as appropriate, by various techniques such as NMR, EPR, near-IR, and UV-vis. The fluoflavinate ligand strongly mediates electronic communication between the dimetal units, and the mixed valence species 2 can be described as electronically delocalized. Calculations at the DFT level using a variety of functionals support such an assignment and indicate that a strong transition in the NIR for the singly oxidized species can be assigned to the HOMO-1 to SOMO transition.

A far superior synthesis is reported for W(2)(hpp)(4)Cl(2), a key intermediate in the synthesis of the most easily ionized closed-shell molecule W(2)(hpp)(4) (hpp = the anion of the bicyclic guanidine compound 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). At 200 degrees C, the one-pot reaction of the air-stable and commercially available compounds W(CO)(6) and Hhpp in o-dichlorobenzene produces W(2)(hpp)(4)Cl(2) in multigram quantities with isolated yields of over 90%. At lower temperatures, the reaction can lead to other compounds such as W(Hhpp)(2)(CO)(4) or W(2)(mu-CO)(2)(mu-hpp)(2)(eta(2)-hpp)(2), which are isolable in good purity depending upon the specific conditions employed. These compounds provide insight into the reaction pathway to W(2)(hpp)(4)Cl(2) and W(2)(hpp)(4). Two additional derivatives, W(2)(hpp)(4)X(2) where X is PF(6)(-) or the anion tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB), have also been synthesized and structurally characterized. A comparison of the electrode potentials of W(2)(mu-CO)(2)(mu-hpp)(2)(eta(2)-hpp)(2) and the di-p-anisylformamidinate analogue shows that oxidation of the hpp compound is significantly displaced (1.12 V) and shows that the bicyclic guanidinate ligand is considerably better than the formamidinate anion at stabilizing high oxidation states. A differential pulse voltammogram of W(2)(hpp)(4)(TFPB)(2) in THF shows two reduction processes with an E(1/2) of -0.97 V for the first and -1.81 V (vs Ag/AgCl) for the second. DFT calculations on the W(2)(hpp)(4)(2+) units in W(2)(hpp)(4)X(2) compounds show that the metal-metal bonding orbitals are destabilized by the axial ligands, which accounts for significant variations in the W-W distances. The low-energy gas-phase ionizations of W(2)(hpp)(4) are also reported and discussed.

We report a dirhodium paddlewheel compound which has an Rh2(5+) core enveloped by four guanidinate ligands and an axially coordinated bromine atom; Rh2(hpp)4Br crystallizes as a 1-D chain with a Rh-Rh distance of 2.430(3) è and a Rh-Rh bond order of 1.5 (hpp = the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2a]pyrimidine).

Two enantiopure molecular loops, RR-[cis-Rh2(C6H4PPh2)2(py)2O2C(CF2)(n)CO2]2 (1, n = 2 and 2, n = 3) have been made from the reaction in CH2Cl2 and CH3OH of the inherently chiral dirhodium compound, R-[cis-Rh2(C6H4PPh2)2(CH3CN)6](BF4)2, and HO2C(CF2)(n)CO2H in the presence of an excess of pyridine. Single-crystal structure analyses reveal that each of these compounds is composed of two R-cis-Rh2(C6H4PPh2)2(ax-py)2(2+) units, and two equatorial perfluorodicarboxylate linkers, which form a loop oligomer. The 1H, 19F, and 31P[1H] NMR spectra in CDCl3 and C5D5N indicate that only one type of highly symmetric species exists in each solution, which is consistent with the solid-state structures.

Enantiomers of the orthometalated dirhodium compound cis-Rh2(C6H4PPh2)2(OAc)2(HOAc)2 (R-1 and S-1) were prepared from carboxylate exchange reactions of the resolved diasteroisomers of cis-Rh2(C6H4PPh2)2(protos)2(H2O)2 (protos = N-4-methylphenylsulfonyl-l-proline anion) and acetic acid. These compounds react with excess Me3OBF4 in CH3CN, producing the enantiomers of [cis-Rh2(C6H4PPh2)2(CH3CN)6](BF4)2 (R-2 and S-2) which have six labile and replaceable CH3CN ligands in equatorial and axial positions. Reactions of R-2 and S-2 with tetraethylammonium salts of the linear dicarboxylic acids, terephthalic acid (HO2CC6H4CO2H), oxalic acid (HO2CCO2H), and 4,4'-diphenyl-dicarboxylic acid (HO2CC6H4C6H4CO2H) afford the enantiopure triangular supramolecules [cis-Rh2(C6H4PPh2)2(O2CC6H4CO2)(py)2]3, RRR-3 and SSS-3, Rh6(cis-C6H4PPh2)6(O2CCO2)3(py)5(CH2Cl2), RRR-4 and SSS-4, and Rh6(cis-C6H4PPh2)6(O2CC6H4C6H4CO2)3(py)4(CH2Cl2)2, RRR-5 and SSS-5, respectively. The absolute structures of each of the enantiomers of 1, 3, 4, and 5 were determined by X-ray diffraction analyses. The enantiomers of 3, 4, and 5 were found to be enantiomorphically isostructural, whereas R-1 and S-1 crystallized in different space groups. In 4 and 5, CH2Cl2 molecules coordinate to rhodium atoms in the axial positions. The 1H and 31P[1H] NMR spectra of all compounds are reported. The triangular compounds are redox-active, and their electrochemistry is also discussed. An assay of the catalytic activity/selectivity performance of the triangles for typical metal carbene transformation, using the model intermolecular cyclopropanation of styrene with ethyl diazoacetate in both homogeneous and heterogeneous phases, show that these chiral triangles are very active and have remarkable selectivity when compared with simple Rh2 paddle-wheel catalysts with chiral amidate ligands.

A carceplex with T symmetry of the type A(4)B(6) has been synthesized enantiospecifically by employing the trianion of benzene-1,3,5-tricarboxylic (trimesic) acid as A and the R-cis-Rh(2)(C(6)H(4)PPh(2))(2)(2+) cation as B. The chiral (C(2)) B units abolish the symmetry planes required for T(d) symmetry, thus leaving only the eight C(3) and three C(2) rotations of the group T. Racemization is impossible under any chemically interesting conditions. This would appear to be only the third case where both preselection of the desired enantiomer and enantiostability based on covalent bonding are achieved.

We present the synthesis, as well as the structural and magnetic characterization, of [Ru2(D(3,5-Cl2Ph)F)4Cl(0.5H2O)].C6H14 (D(3,5-Cl2Ph)F = N,N'-di(3,5-dichlorophenyl)formamidinate), a Ru2(5+) compound having a 4B(2u) ground state derived from a sigma2pi4delta2pi2delta electron configuration. The persistence of this configuration from 27 to 300 K is shown by the invariance of the Ru-Ru distance. Orientation-dependent magnetic susceptibility (chiT) and magnetization (M(H)) data are in accord with a spin quartet ground state with large magnetocrystalline anisotropy associated with a large axial zero-field splitting (D) parameter. Theoretical fits to chiT and M(H) plots yielded D/kB = +114 K, implying an S = +/-1/2 Kramers doublet ground state at low temperature. Single-crystal and powder EPR data are consistent with this result, as the only observed transition is between the M(s) = +/1/2 Zeeman levels. The g values are g(perpendicular) = 2.182, g(parallel) = 1.970, and D = 79.8 cm(-1). The totality of the results demands D >> 0.

Reactions of Pd3(OAc)6 with lithium salts of mononegative bidentate N,N-ligands, L, of various types, such as formamidinates, benzamidinates, triazinates, and guanidinates, were investigated in a search for ways to obtain Pd2(4+) compounds that could serve as precursors to paddlewheel complexes with a metal-metal bond and a Pd2(5+) core. It was found that the reactions are complex and that either square planar mononuclear or dinuclear species may be formed depending on the reaction conditions or the method of isolation. For Pd2L4 compounds, alpha and beta isomers were sometimes obtainable. In the alpha isomer, all N,N-ligands serve as bridges, whereas in the beta isomer, two ligands bridge the Pd2(4+) unit and each of the other two chelate to a metal atom. Electrochemistry shows that the paddlewheel compounds Pd2(TolNC(H)NTol)4, Pd2(PhNC(Ph)NPh)4, and Pd2(PhNC(Ph)NPh)3(OAc) and the orthometalated complex cis-Pd2[eta2-C6H4NC(Ph)N(H)Ph]2(mu-OAc)2 have reversible oxidation waves between 0.70 and 0.92 V vs Ag/AgCl, which makes them good candidates for chemical oxidation.

A new synthetic path, far superior to either of those previously available, to the W2(hpp)4 molecule (Hhpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) is reported. The reaction of W(CO)6 with Hhpp in o-dichlorobenzene at 200 degrees C produces W2(hpp)4Cl2 in a one-pot reaction in over 90% yield. This compound is stable and easily stored for further use, and it can be efficiently reduced in a one-step reaction to the title compound W2(hpp)4.

Background: The phosphoinositide 3-kinase (PI3K/Akt) pathway transduces signals initiated from growth factors. Previously, we identified an important role for PI3K/Akt in colon cancer progression. The purpose of this study was to determine (1) whether short interfering RNA (siRNA) directed to PI3K/Akt components can render colon cancer cells sensitive to treatment with tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) and (2) the cellular mechanisms contributing to the enhanced sensitivity., Methods: Human colon cancer cells KM20 and KM12C (both TRAIL resistant) were transfected with siRNA directed against the PI3K p85alpha regulatory subunit Akt1 or nontargeting control sequence and then treated with TRAIL (100 ng/mL) or vehicle. A ribonuclease protection assay was performed to assess changes in TRAIL receptor expression. Protein was extracted and analyzed by Western blot for expression of cleavage of TRAIL receptors (death receptor (DR) 4 and 5), caspase-3, caspase-8, and BID. Apoptosis was measured by enzyme-linked immunosorbent assay of DNA fragmentation., Results: Combination treatment with p85alpha or Akt1 siRNA and TRAIL increased apoptosis in KM20 and KM12C cells, compared with TRAIL alone; these results were corroborated further by complete inhibition of apoptosis by Z-acetyl-Asp-Glu-Val-Asp-(DEVD)-fmk, a caspase-3 inhibitor. Furthermore, siRNA-mediated PI3K pathway inhibition resulted in increased expression of the TRAIL death receptors 4 and 5., Conclusions: Inhibition of PI3K/Akt by RNA interference sensitizes resistant colon cancer cells to TRAIL-induced cell death through the induction of TRAIL receptors and activation of caspase-3 and caspase-8. Agents that selectively target the PI3K/Akt pathway may enhance the effects of chemotherapeutic agents and provide novel adjuvant treatment for selected colon cancers.

Reaction of activated palladium metal with a HNO3/acetic acid mixture produces both orange Pd3(OAc)6, 1, and purple Pd3(OAc)5(NO2), 2. Compound has a trinuclear structure derived from that of the well-known triangular complex 1 in which one acetate group has been replaced by a nitrite group which is bonded to one palladium atom by the nitrogen atom and to another Pd atom using one of the oxygen atoms. Highly pure 1 can be made by continuous removal of the nitric oxides from the reaction mixture using a flow of N2. 1H NMR spectra of solutions of 1 in CDCl3 and C6D6 show several signals of various intensities when a small amount of water is present in the deuterated solvents but only one signal when the solvents are thoroughly dried. These results are consistent with the occurrence of one or more hydrolysis processes when the solvents contain water and suggest that hypotheses about various [Pd(OAc)2]n aggregates that have previously been brought forward in the literature to explain the complexity of the spectrum of 1 are unnecessary, especially for nonpolar solvents. Compound 2 does not hydrolyze, and in wet or dried solvents shows a 1H NMR spectrum that consists of five equal-intensity signals due to the five nonequivalent acetate groups.

The magnetic and structural properties of two Ru2(DArF)4Cl compounds, where DArF is the anion of a diaryl formamidine, are presented here. The compounds with Ar = p-anisyl and m-anisyl both show temperature dependence of chiT (chi = molar magnetic susceptibility), but for different reasons. For the para compound, there is a Boltzmann distribution between a pi*3 ground state and a delta*pi*2 upper state, and this is confirmed by a temperature dependence of the Ru-Ru bond length: 2.4471(5) A at 23 K and 2.3968(5) A at 300 K. For the meta compound, a delta*pi*2 configuration persists over the range of 23-300 K as shown by an invariant Ru-Ru bond length, but the chiT drops with decreasing temperature owing to zero-field splitting of a 4B2u ground state.

The X-ray crystallographic structures, the magnetic susceptibilities from 2 to 300 K, and a theoretical analysis of the magnetism for a triangular and a tetranuclear molecule consisting of linked high-spin cobalt(II) centers are described. The interpretation of the magnetic data for the triangular compound [Co(depa)Cl](3) (depa is the anion of 2,2'-(bis-4-ethylpyridyl)amine), which has tetrahedrally coordinated Co(2+) ions, entails isotropic antiferromagnetic exchange interaction and antisymmetric exchange acting within the two low-lying spin doublets. Two strong isotropic ferromagnetic interactions have been modeled in the cuboidal compound Co(4)(DPM)(4)(CH(3)O)(4)(CH(3)OH)(4) (DPM represents the anion of dipivaloylmethane), which has octahedral coordination, and the system can be approximately considered as two weakly coupled S = 3 species.

The title compound, [Ru2(C13H11N2)3(C2H3O2)(C2H3N)]BF4.0.5CH2Cl2 or [Ru2(mu-DPhF)3(mu-O2CMe)(MeCN)]BF4.0.5CH2Cl2, where DPhF is N,N'-diphenylformamidinate, crystallized as dark-blue block-shaped crystals. In the unit cell, the diruthenium cation lies on a general position, and the BF4- anions reside on two independent special positions with crystallographic twofold symmetry. Disorder was observed for one of the phenyl groups in the formamidinate ligand, the axial acetonitrile molecule and the interstitial dichloromethane molecule. The compound, which exhibits a long Ru-Ru bond of 2.4131 (5) A, is the first {Ru2}5+ formamidinate species that is both equatorially and axially functionalized so that it can be used as a precursor for polymeric paramagnetic supramolecular assemblies.

The title compound, [Ru2(C2H3O2)4(C15H16N2O2)2], lies on a crystallographic inversion center and exhibits an Ru-Ru bond length of 2.2847 (8) A. There are weak intramolecular hydrogen-bonding interactions between the N1,N2-di-p-anisylformamidine (HDAniF) ligands and the bridging acetate ligands. The molecule is one of the few examples of a crystallographically characterized axial bis-adduct of a {Ru2}4+ complex with two N-donor ligands.

Variable temperature magnetic studies of the Ru(2)(6+) guanidinate compounds Ru(2)(hpp)(4)Cl(2) (1) and Ru(2)(hpp)(4)(CF(3)SO(3))(2) (2) show that they are paramagnetic with two unpaired electrons at room temperature and that they appear essentially diamagnetic at 2 K. In neither compound do the Ru-Ru distances vary by more than 0.008(1) A from 27 to 296 K. This argues strongly that the ground state electronic configuration remains constant over this temperature range and that the decrease in magnetism as the temperature is lowered must be attributable to zero-field splitting of the (3)A(2g) ground state arising from the electronic configuration sigma(2)pi(4)delta(2)pi(2). The Ru-Ru distance in 1 is about 0.04-0.05 A longer than that in 2 which indicates that the Ru(2)(hpp)(4)(2+) core is quite sensitive to the nature of the axial ligands. The electronic spectra show three absorption bands for each compound.

Reaction of racemic cis-Rh(2)(C(6)H(4)PPh(2))(2)(OAc)(2)(HOAc)(2) with excess Me(3)OBF(4) in CH(3)CN results in the formation of racemic cis-[Rh(2)(C(6)H(4)PPh(2))(2)(CH(3)CN)(6)](BF(4))(2).0.5H(2)O (1.0.5H(2)O), an ionic dirhodium complex which has two cisoid nonlabile orthometalated phosphine bridging anions and six labile CH(3)CN ligands in equatorial and axial positions. Reactions of 1 with tetraethylammonium salts of the linear dicarboxylates, oxalate, terephthalate, and 4,4'-biphenyl-dicarboxylate, in organic solvents, produced racemic crystals of the triangular compounds [Rh(2)(C(6)H(4)PPh(2))(2)](3)(C(2)O(4))(3)(py)(6).6MeOH.H(2)O (2.6MeOH.H(2)O), [Rh(2)(C(6)H(4)PPh(2))(2)](3)(O(2)CC(6)H(4)CO(2))(3)(DMF)(6).6.5DMF.0.5H(2)O (3.6.5DMF.0.5H(2)O), and [Rh(2)(C(6)H(4)PPh(2))(2)](3)(O(2)CC(6)H(4)C(6)H(4)CO(2))(3)(py)(6).4.5CH(3)OH.0.75H(2)O (4.4.5CH(3)OH.0.75H(2)O), respectively. All compounds are electrochemically active. The relative chiralities of the dirhodium units in each triangle have been established using a combination of data from X-ray crystallography and (31)P NMR spectroscopy.

Reactions of Ru(2)(O(2)CMe)(4)Cl with two formamidines, HDXyl(2,6)F = N,N'-di(2,6-xylyl)formamidine and HDAniF = N,N'-di(p-anisyl)formamidine, have been investigated with the idea of synthesizing compounds with a mixed set of ligands having different labilities to be used as precursors of paramagnetic, higher-order assemblies. Depending on the formamidine and the reaction conditions, several Ru(2)(5+) compounds of the type Ru(2)(O(2)CMe)(4)(-)(n)(DArF)(n)Cl (DArF = anion of an N,N'-diarylformamidine) have been isolated. With the bulky formamidine HXyl(2,6)F, the compounds Ru(2)(O(2)CMe)(3)(DXyl(2,6)F)Cl (1) and trans-Ru(2)(O(2)CMe)(2)(DXyl(2,6)F)(2)Cl (2) were obtained. From reactions with appropriate amounts of HDAniF in THF and in the presence of NEt(3) and LiCl, complexes of the general type Ru(2)(O(2)CMe)(4)(-)(n)(DArF)(n)Cl (n = 1-4) were selectively obtained. For n = 2, only the cis isomer was obtained. The choice of solvent in reactions of Ru(2)(O(2)CMe)(4)Cl and HDAniF is of great importance. Toluene favored the formation of the fully substituted Ru(2)(5+) complex Ru(2)(DAniF)(4)Cl (3), whereas MeOH resulted in a disproportionation reaction that gave the edge-sharing bioctahedral Ru(3+)Ru(3+) complex [trans-Ru(2)(mu-OMe)(2)(mu-O(2)CMe)(2)(HDAniF)(4)]Cl(2) (6) and the Ru(2)(4+) complex Ru(2)(DAniF)(4) (7). Complexes 6 and 7 with an Ru(2)(6+) and Ru(2)(4+) core, respectively, are diamagnetic, whereas all Ru(2)(5+) complexes are paramagnetic with sigma(2)pi(4)delta(2)(pi*delta*)(3) ground-state electronic configurations and large zero-field splitting contributions. All compounds show rich and complex electrochemical behavior.

Very strong electronic communication, manifested in a K(C) value of ca. 10(9), has been found in a system of three compounds separated by one electron oxidation where each compound contains two metal-metal bonded Mo(2)(n+) units linked by a dimethyloxamidate anion, CH(3)N(O)C-C(O)NCH(3)(2)(-). The Mo-Mo distances increase as the oxidation state increases and the bond order decreases, while the diamagnetic, doubly oxidized species becomes essentially planar and resembles a naphthalene molecule. Calculations at the DFT level indicate that a strong transition in the near-IR region, shown by the singly oxidized and paramagnetic species, is best described as a HOMO-1 --> SOMO transition.

Reactions of W(CO)(6) with formamidines contrast with those of Mo(CO)(6) and Cr(CO)(6) in that the former do not yield quadruply bonded dimetal species. From the reaction of W(CO)(6) with HDAniF (HDAniF = N,N'-di-p-anisylformamidine), several new ditungsten carbonyl compounds (W(2)(mu-CO)(2)(mu-DAniF)(2)(eta(2)-DAniF)(2) (1), W(2)(mu-CO)(2)(mu-DAniF)(2)(eta(2)-DAniF)(eta(2)-CH(2)DAniF) (2), and W(2)(mu-CO)(mu-CNC(6)H(4)OCH(3))(mu-DAniF)(2)(eta(2)-DAniF)(2) (3)) have been isolated and fully characterized. In 2, CH(2)DAniF represents a DAniF ligand in which a methylene group has been added to one of the nitrogen atoms. This ligand binds to the tungsten atom using a nitrogen and a carbon atom. Compound 1 has a tungsten-tungsten bond distance of 2.476(1) A and a planar W(2)(mu-CO)(2) core structure which has C(2)(h)() symmetry with short and long W-C bond distances (1.99(1) and 2.28(1) A, respectively). DFT calculations on a model of 1 indicate that (a) the C(2)(h)() instead of D(2)(h)() symmetry of the ditungsten core may be attributed to W --> CO pi back-bonding interactions and (b) the bond between the tungsten atoms may be formulated as a double bond. The new tetragonal paddlewheel compound W(2)(DAniF)(4) (4) and the edge-sharing bioctahedron W(2)(mu-O)(mu-NC(6)H(3)Cl(2))(mu-D(Cl)PhF)(2)(eta(2)-D(Cl)PhF)(2) (5) (D(Cl)PhF = N,N'-di-(3,5-dichlorophenyl)formamidinate) have also been prepared.

Structural studies of pentachromium and pentacobalt extended metal atom chain (EMAC) systems are presented in which the metal chains are helically wrapped by either the pentadentate dianion tripyridyldiamide (tpda) or its diethyl-substituted analogue bis(4-ethyl-2-pyridylamido)pyridine (etpda). The compound Cr(5)(tpda)(4)(NCS)(2), has alternating long and short Cr-Cr distances, contrary to recent reports that describe it as symmetrical with essentially equally spaced chromium atoms. The linear Cr(5)(10+) chain is composed of two Cr(2)(4+) quadruply bonded units and an isolated high spin Cr(II) unit. The new compounds Cr(5)(etpda)(4)Cl(2), [Cr(5)(etpda)(4)FCl]PF(6), and Co(5)(etpda)(4)(NCS)(2)() employ the etpda ligand as "insulation" around a central pentametal-atom "wire." Compound, like all other oxidized pentachromium compounds, has very disparate alternating short-long-short-long Cr-Cr distances, 2.032(3) A, 2.560(6) A, 1.873(5) A, and 2.509(4) A. Compound shows a nearly uniform spacing of the Co atoms, although the outer Co-Co distances (2.279[4] A) are slightly longer than the inner ones (2.239[4] A).

Background: Phosphatidylinositol 3-kinase (PI3K), acting through the downstream kinase AKT, regulates a number of cellular processes such as cell growth and survival. Poorly differentiated colon cancers are characterized by increased integrin-mediated extracellular matrix interactions; disruption of this integrin-mediated adhesion leads to apoptosis and involves reduced PI3K activity. The purpose of this study was to determine: (1) the role of alpha5beta1 integrin expression on PI3K activity, and (2) whether blockade of alpha5beta1 integrin decreases colon cancer cell adhesion and increases apoptosis., Methods: Human colon cancer cells were treated with anti-alpha5 integrin antibody, anti-beta1 integrin antibody, the PI3K inhibitor LY294002 (20 micromol/L), or wortmannin (400 nmol/L). Expression and function of alpha5 were quantitated by FACS analysis and cell adhesion assay, respectively. DNA fragmentation was measured to assess apoptosis. Protein was extracted to determine phosphorylated AKT (pAKT) expression as a measure of PI3K activity., Results: Increased pAKT and alpha5 integrin expression were noted in the colon cancer cells; blockade of alpha5 integrin decreased alpha5 integrin and pAKT expression and decreased cell adhesion. Moreover, PI3K inhibition resulted in decreased alpha5 integrin expression. In contrast, treatment with anti-beta1 integrin antibody produced no change in pAKT expression or cell number., Conclusion: Our results are the first to show that blockade of cell surface alpha5 integrin expression decreases PI3K activity, inhibits colon cancer cell attachment, and induces apoptosis. These findings suggest that agents which selectively target alpha5 integrin subunit expression may enhance the effects of standard chemotherapeutic agents and provide novel adjuvant treatment for selected colon cancers., (Copyright 2004 Elsevier Inc.)

The preparation, properties, and crystal structures of 12 trichromium extended metal atom chain (EMAC) compounds of the type Cr(3)(L)(4)X(2) (L = equatorial ligands dipyridylamide (dpa) or di-4,4'-ethyl-2,2'-pyridylamide (depa), and X = axial ligands, e.g., halide or pseudohalide ions) with large variations in metal-metal distances are reported here. These complexes, which belong to a broad class of fundamentally interesting trinuclear molecules over which the electrons may or may not be delocalized, pose significant theoretical and experimental challenges which are dealt with in this report. Complexes with strongly donating axial or equatorial ligands tend to favor a symmetrical (D(4)) molecular structure, while more weakly donating ligands give rise to unsymmetrical (C(4)) structures; the physical properties of these two classes of compounds are discussed fully, and important comparisons with a reported DFT model of the electronic structures of the compounds are made.

The preparation of additional and useful building blocks for the construction of supramolecular entities with quadruply bonded Mo(2)(4+) units has been explored, and five new mixed-ligand complexes with three types of ligands and various basicities are reported. The ligands used were the DAniF (N,N'-di-p-anisylformamidinate) anion, the acetate anion, and neutral acetonitrile molecules. The formamidinate ligands are the least labile, and the acetonitrile molecules are the most labile. This difference as well as a relatively strong trans directing influence by the formamidinate anions in ligand substitution reactions allows designed synthesis of various mixed-ligand building blocks, including rare pairs of cis and trans isomers. The new compounds are cis-Mo(2)(DAniF)(2)(O(2)CCH(3))(2) (1), trans-Mo(2)(DAniF)(2)(O(2)CCH(3))(2) (2), trans-[Mo(2)(DAniF)(2)(O(2)CCH(3))(CH(3)CN(eq)())(2)]BF(4) (3), trans-[Mo(2)(DAniF)(2)(CH(3)CN(eq)())(4)](BF(4))(2) (4), and [Mo(2)(O(2)CH(3))(CH(3)CN(eq)())(6)(CH(3)CN(ax)())](BF(4))(3) (5), where eq and ax designate equatorial and axial ligands, respectively. A comparison with some previously synthesized complexes is given along with a discussion of the overall reactivity of all compounds.

Efficient syntheses are reported for incorporating trimetal units of the type M(3)(dpa)(4)(2+) (M = Cr, Co, Ni, and dpa = 2,2'-dipyridylamide) into polyalkynyl assemblies to give the prototypical bis-phenylacetylide complexes M(3)(dpa)(4)(CCPh)(2). Reactions of M(3)(dpa)(4)Cl(2) with LiCCPh have led only to mixtures of products which cocrystallize forming materials of the composition M(3)(dpa)(4)(CCPh)(x)()Cl(2)(-)(x)(). Here we report that acetonitrile complexes [M(3)(dpa)(4)(NCCH(3))(2)](PF(6))(2) react cleanly with LiCCPh in MeCN to afford the desired target molecules in 40-60% yield and in excellent purity. Isolation of the mixed ligand complex [Co(3)(dpa)(4)(NCCH(3))(CCPh)]PF(6) has been accomplished, which suggests that these reactions are stepwise and that it will be possible to synthesize mixed acetylide complexes (i.e., M(3)(dpa)(4)(CCR)(CCR')) via this method.

It is shown that a spheroidal carceplex can be assembled by linking two bowl-shaped calix[4]arenes via four dimetal units, (DAniF)(2)Rh(2) (DAniF = N,N'-di-p-anisylformamidinate), with a molecule (diethyl ether) or a cation (tetraethylammonium ion) trapped inside. The tetraethylammonium carceplex, 1b, has been characterized by X-ray crystallography, (1)H NMR, IR, and mass spectrometry. The tetraethylammonium ion fits snugly in the interior of the spheroidal carceplex. A two-fold axis of the tetrahedral cation coincides with the idealized four-fold axis of the cage, and the cation is disordered over two rotational orientations. Only one axial position on each dirhodium unit is occupied by a ligand, CH(3)CN or H(2)O. The carceplex is very stable, and the axial ligands can be exchanged in single crystals without disrupting the crystallinity of the samples. In this way, a red crystal of the complex with all axial positions occupied by acetonitrile can be transformed to a green crystal of the complex with two axial positions having acetonitrile and the other two having water by simply putting the crystal in contact with distilled water. The calix[4]arene used to make the carciplex structure is 25,26,27,28-tetra-n-propoxycalix[4]arene-5,11,17,23-tetracarboxylic acid. By employing 25,26,27,28-tetrapropoxy-5,17-dibromo-calix[4]arene-11,23-dicarboxylic acid, two 1:1 dimetal:calixarene compounds have also been made and characterized: 2, cis-Rh(2)(DAniF)(2)(calix)(CH(3)OH), and 3, cis-Mo(2)(DAniF)(2)(calix). The Rh-Rh distances in 1b are in the range of 2.410(2)-2.428(2) A, that in 2 is 2.4383(4) A, and the Mo-Mo distance in 3 is 2.0931(4) A.

Reactions of Mo(2)(O(2)CCH(3))(DAniF)(3), DAniF = N,N'-di-p-anisylformamidinate, with oxamidate dianions [ArNC(O)C(O)NAr](2-), Ar = C(6)H(5) and p-anisyl, give pairs of isomeric compounds where the [Mo(2)] units are bridged by the oxamidate anions. For the alpha isomers, the C-C unit of the dianion is nearly perpendicular to the Mo-Mo bonds, and these are essentially perpendicular to each other. For the beta isomers, the corresponding C-C unit and the Mo-Mo bonds are essentially parallel to each other. Each type of isomer is stable in solution. The electronic communication as measured by the DeltaE(1/2) for the oxidation of each of the Mo(2) units is significantly better for the beta isomers. This is supported also by the appearance of what is conventionally called an intervalence charge-transfer band in the near infrared region upon oxidation of the beta isomers but not the alpha isomers. Molecular mechanics and DFT calculations help explain the relative conformations in the alpha isomers and the relative energy differences between the alpha and beta isomers.

Two previously reported compounds [Mo(2)](CH(3)O)(2)M(CH(3)O)(2)[Mo(2)] (Cotton, F. A.; Liu, C. Y.; Murillo, C. A.; Wang, X. Inorg. Chem. 2003, 42, 4619), in which [Mo(2)] is an abbreviation for the quadruply bonded Mo(2)(4+) unit embraced by three (p-anisyl)NC(H)N(p-anisyl) anions and M = Zn (1) or Co (2), have been chemically oxidized. One-electron oxidation products [Mo(2)](CH(3)O)(2)M(CH(3)O)(2)[Mo(2)](PF(6)) (3, M = Zn; 4, M = Co) and the two-electron oxidation product [Mo(2)](CH(3)O)(2)Zn(CH(3)O)(OH)[Mo(2)](PF(6))(2) (5) have been isolated and structurally characterized. As expected, oxidations occur at the dimolybdenum units. The mono-charged cations in 3 and 4 have asymmetric molecular structures with two distinct [Mo(2)] units. In each case, one of the [Mo(2)] units has a lengthened Mo-Mo bond distance of 2.151[1] A, as expected for one-electron oxidation, whereas the other remains unchanged at 2.115[1] A. These correspond to bond orders of 3.5 (sigma(2)pi(4)delta(1)) and 4.0 (sigma(2)pi(4)delta(2)), respectively. The crystallographic results thus show unambiguously that in the crystalline state, the mixed-valence compounds (3 and 4) are electronically localized and the unpaired electron is trapped on one [Mo(2)] unit. These results are supported by the EPR spectra. The doubly oxidized compound 5 has two equivalent [Mo(2)] units, both with a Mo-Mo bond distance of 2.149[1] A. EPR and magnetic susceptibility measurements for 5 indicate that there is no significant ferromagnetic or antiferromagnetic spin coupling and the species is valence-trapped.

We report here the synthesis and characterization of seven new divanadium compounds with the paddlewheel geometry bridged by nitrogen-donating ligands. Five of these contain the diamagnetic V(2)(4+) core with short V-V distances of less than 2.0 A, consistent with a formal triple bond. The V-V distances vary with the basicity of the bridging ligands; more basic ligands such as those of the guanidinate type have the shorter metal-metal separations, and those with the less basic formamidinate groups have longer separations. One compound, V(2)(DPhF)(4) (DPhF = the anion of N,N'-diphenylformamidine), has been reduced by one electron, and two structures, [K(THF)(3)]V(2)(DPhF)(4) and [K(18-crown-6)(THF)(2)]V(2)(DPhF)(4), have been obtained. These have an unprecedented V(2)(3+) core where the formal oxidation state of each vanadium atom is +1.5. The decrease in V-V bond distance and the multiline EPR spectrum in the reduced species provide evidence that these two molecules contain a bond of order 3.5.

The first oxidation of a species derived from a compound having two linked, quadruply-bonded Mo2 units has been performed and [[cis-Mo2(DAniF)2]2(mu-Cl)4]PF6, 2, has been isolated and characterized in many ways; it has one unpaired electron and a fully delocalized structure where the Mo-Mo distances increase from 2.1191(4) A in the reduced species to 2.1453(3) A in 2 and the Kc of 1.3 x 10(9) is three orders of magnitude larger than that of the Creutz-Taube ion.

The reaction of Ru(2)(mu-O(2)CMe)(4)Cl with approximately 2.5 equiv of HDAniF (HDAniF = N,N'-di(p-anisyl)formamidine) in refluxing THF resulted in the synthesis of cis-Ru(2)(mu-DAniF)(2)(mu-O(2)CMe)(2)Cl (1). This Ru(2)(5+)complex, which has two labile acetate groups occupying two equatorial cisoid positions, was used for the construction of discrete paramagnetic supramolecular arrays. Subsequent reactions of 1 with HO(2)C-CO(2)H (oxalic acid) and 1,4-HO(2)C-C(6)H(4)-CO(2)H (terephthalic acid) followed by recrystallization from 1,2-C(2)H(4)Cl(2)/hexanes solutions containing wet MeCN or 4-Bu(t)py (4-tert-butylpyridine) gave crystals of [[is-Ru(2)(mu-DAniF)(2)Cl(H(2)O)]mu-oxalate)](4).MeCN.2(C(6)H(14)).12(H(2)O) (2) and [[is-Ru(2)(mu-DAniF)(2)Cl(0.646)(4-Bu(t)py)(1.354)]mu-terephthlate)](4)Cl(1.414).17(1,2-C(2)H(4)Cl(2)).C(6)H(14) (3), respectively. These are the first polygonal supramolecular assemblies consisting of paramagnetic M(2) units at each apex, where M(2) = Ru(2)(5+). Compounds 2 and 3 have been structurally characterized, and their electrochemistry and magnetic properties have been studied. These studies have confirmed that oxalate linkers are better than the terephthalate linkers in effecting electronic and magnetic coupling.

Two compounds of a new type, [Mo(2)](CH(3)O)(2)M(CH(3)O)(2)[Mo(2)] where [Mo(2)] is an abbreviation for Mo(2)[(p-MeOC(6)H(4))NCHN(p-MeOC(6)H(4))](3) and M = Zn (1) and Co (2), are reported. Discrete [M(OR)(4)](2-) ions, either as such or in the mu(2),eta(4) role, have not heretofore been described. In these compounds they have distorted tetrahedral structures and bridge two [Mo(2)] groups in much the same way as did SO(4)(2-), MoO(4)(2-), and WO(4)(2-) ions in other recently reported compounds (Cotton, F. A.; Donahue, J. P.; Murillo, C. A. Inorg. Chem. 2001, 40, 2229). The (1)H NMR spectrum of 1 and the visible spectrum and magnetic properties of 2 are consistent with these structures. The M(OCH(3))(4) bridges are moderately effective in coupling the two [Mo(2)] redox centers. Compounds 1 and 2 may also be viewed as having Zn(II) and Co(II) centers tetrahedrally coordinated by the bidentate ligand [Mo(2)[(p-MeOC(6)H(4))NCHN(p-MeOC(6)H(4))](3)(OMe)(2)](-). From that point of view they may be compared with Zn(DPM)(2) and Co(DPM)(2) (3), where DPM is the anion of dipivaloylmethane. For purposes of comparison, 3 has been fully characterized structurally, spectroscopically, and magnetically. Close analogies between 2 and 3 are shown to exist.