Open-Ended Metallodithiolene Complexes with the 1,2,4,5-Tetrakis(diphenylphosphino)benzene Ligand: Modular Building Elements for the Synthesis of Multimetal Complexes.

Open-ended, singly metalated dithiolene complexes with 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) are prepared either by ligand transfer to [Cl2M(tpbz)] from (R2C2S2)SnR'2 (R = CN, R' = Me; R = Me, R' = nBu) or by a direct reaction between tpbz and [M(S2C2R2)2] (M = Ni, Pd, Pt; R = Ph, p-anisyl) in a 1:1 ratio. The formation of dimetallic [(R2C2S2)M(tpbz)M(S2C2R2)] attends these syntheses in modest amounts, but the open-ended compounds are readily separated by silica chromatography. As affirmed by X-ray crystallographic characterization of numerous members of the set, the [(R2C2S2)M(tpbz)] compounds show dithiolene ligands in their fully reduced ene-1,2-dithiolate form conjoined with divalent Group 10 ions. Minor amounts of octahedral [(Ph2C2S2)2PtIV(tpbz)], a presumed intermediate, are isolated from the preparation of [(Ph2C2S2)PtII(tpbz)]. Heterodimetallic [(Ph2C2S2)Pt(tpbz)Ni(S2C2Me2)] is prepared from [(Ph2C2S2)PtII(tpbz)]; its cyclic voltammogram, upon anodic scanning, shows two pairs of closely spaced, but resolved, 1e- oxidations corresponding first to [R2C2S22-] - 1e- → [R2C2S•S-] and then to [R2C2S•S-] - 1e- → [R2(C═S)2]. The open diphosphine of [(R2C2S2)M(tpbz)] can be oxidized to afford open-ended [(R2C2S2)M(tpbzE2)] (E = O, S). Synthesis of the octahedral [(dppbO2)3Ni][I3]2 [dppbO2 = 1,2-bis(diphenylphosphoryl)benzene] suggests that the steric profile of [(R2C2S2)M(tpbzE2)] is moderated enough that three could be accommodated as ligands around a metal ion.

Zn Coordination and the Identity of the Halide Ancillary Ligand Dramatically Influence the Excited-State Dynamics and Bimolecular Reactions of 2,3-Di(pyridin-2-yl)benzo[g]quinoxaline.

The optical properties of coordination complexes with ligands containing nitrogen heterocycles have been extensively studied for decades. One subclass of these materials, metal complexes utilizing substituted pyrazines and quinoxalines as ligands, has been employed in a variety of photochemical applications ranging from photodynamic therapy to organic light-emitting diodes. A vast majority of this work focuses on characterization of the metal-to-ligand charge-transfer states in these metal complexes; however, literature reports rarely investigate the photophysics of the parent pyrazine or quinoxaline ligand or perform control experiments utilizing metal complexes that lack low-lying charge-transfer (CT) states in order to determine how metal-atom coordination influences the photophysical properties of the ligand. With this in mind, we examined the steady-state and time-resolved photophysics of 2,3-di(pyridin-2-yl)benzo[g]quinoxaline (dpb) and explored how the coordination of ZnX2 (X = Cl-, Br-, I-) affects the photophysical properties of dpb. In dpb, we find that the dominant mode of deactivation from the singlet excited state is intersystem crossing (ISC). Coordination of ZnX2 perturbs the relative energies of the ππ* and nπ* excited states of dpb, leading to drastically different rates of ISC as well as radiative and nonradiative decay in the [Zn(dpb)X2] complexes compared to dpb. These differences in the rates change the dominant singlet-excited-state decay pathway from ISC in dpb to a mixture of ISC and fluorescence in [Zn(dpb)Cl2] and [Zn(dpb)Br2] and to nonradiative decay in [Zn(dpb)I2]. Coordination of ZnX2 and the choice of the halide ligand also have profound effects on the rate constants for excited-state bimolecular reactions, including triplet-triplet annihilation and oxygen quenching. These results demonstrate that metal coordination, even in complexes lacking low-lying CT states, and the choice of the ancillary ligand can dramatically alter the photophysical properties of chromophores containing nitrogen heterocycles.

Rationally Designed Redox-Active Au(I) N-Heterocyclic Carbene: An Immunogenic Cell Death Inducer.

Immunogenic cell death (ICD) is a way of reengaging the tumor-specific immune system. ICD can be induced by treatment with chemotherapeutics. However, only a limited number of drugs and other treatment modalities have been shown to elicit the biomarker responses characteristic of ICD and to provide an anticancer benefit in vivo. Here, we report a rationally designed redox-active Au(I) bis-N-heterocyclic carbene that induces ICD both in vitro and in vivo. This work benefits from a synthetic pathway that allows for the facile preparation of asymmetric redox-active Au(I) bis-N-heterocyclic carbenes.

Redox-Active Metallodithiolene Groups Separated by Insulating Tetraphosphinobenzene Spacers.

Compounds of the type [(S2C2R2)M(µ-tpbz)M(S2C2R2)] (R = CN, Me, Ph, p-anisyl; M = Ni, Pd, Pt; tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene) have been prepared by transmetalation with [(S2C2R2)SnR'2] reagents, by direct displacement of dithiolene ligand from [M(S2C2R2)2] with 0.5 equiv of tpbz, or by salt metathesis using Na2[S2C2(CN)2] in conjunction with X2M(µ-tpbz)MX2 (X = halide). X-ray crystallography reveals a range of topologies (undulating, chair, bowed) for the (S2C2)M(P2C6P2)M(S2C2) core. The [(S2C2R2)M(µ-tpbz)M(S2C2R2)] (R = Me, Ph, p-anisyl) compounds support reversible or quasireversible oxidations corresponding to concurrent oxidation of the dithiolene terminal ligands from ene-1,2-dithiolates to radical monoanions, forming [(-S•SC2R2)M(µ-tpbz)M(-S•SC2R2)]2+. The R = Ph and p-anisyl compounds support a second, reversible oxidation of the dithiolene ligands to their α-dithione form. In contrast, [(S2C2(CN)2)Ni(tpbz)Ni(S2C2(CN)2)] sustains only reversible, metal-centered reductions. Spectroscopic examination of [(-S•SC2( p-anisyl)2)Ni(µ-tpbz)Ni(-S•SC2( p-anisyl)2)]2+ by EPR reveals a near degenerate singlet-triplet ground state, with spectral simulation revealing a remarkably small dipolar coupling constant of 18 × 10-4 cm-1 that is representative of an interspin distance of 11.3 Å. This weak interaction is mediated by the rigid tpbz ligand, whose capacity to electronically insulate is an essential quality in the development of molecular-based spintronic devices.

Bis[1,3-bis-(2,4,6-tri-methyl-phen-yl)imidazolium] bis(µ-cis-1,2-di-phenyl-ethene-1,2-di-thiol-ato-κ2S,S':κS)bis-[(cis-1,2-di-phenyl-ethene-1,2-di-thiol-ato-κ2S,S')iron(III)] di-methyl-formamide disolvate.

The mol-ecular structure of the solvated title salt, (C21H25N2)2[Fe2(C14H10S2)4]·2C3H7NO reveals that the anion is situated on a crystallographic inversion center in the triclinic space group P . The title compound crystallizes utilizing a network of weak π-stacking inter-actions of phenyl rings pertaining to the di-thiol-ene unit. Moreover, the acidic imidazolium H atoms [N-C(H)-N] display non-classical hydrogen-bonding inter-actions of the C-H⋯O type to the oxygen atoms of the N,N-dimethyl formamide solvent, and hydrogen atoms on the backbone of imidazolium rings display weak C-H⋯S inter-actions with the di-thiol-ene sulfur atoms.

Redox-switchable ring-closing metathesis: catalyst design, synthesis, and study.

High yielding syntheses of 1-(ferrocenylmethyl)-3-mesitylimidazolium iodide (1) and 1-(ferrocenylmethyl)-3-mesitylimidazol-2-ylidene (2) were developed. Complexation of 2 to [{Ir(cod)Cl}2] (cod=cis,cis-1,5-cyclooctadiene) or [Ru(PCy3)Cl2(=CH-o-O-iPrC6H4)] (Cy=cyclohexyl) afforded 3 ([Ir(2)(cod)Cl]) and 5 ([Ru(2)Cl2(=CH-o-O-iPrC6H4)]), respectively. Complex 4 ([Ir(2)(CO)2Cl]) was obtained by bubbling carbon monoxide through a solution of 3 in CH2Cl2. Spectroelectrochemical IR analysis of 4 revealed that the oxidation of the ferrocene moiety in 2 significantly reduced the electron-donating ability of the N-heterocyclic carbene ligand (ΔTEP=9 cm(-1); TEP=Tolman electronic parameter). The oxidation of 5 with [Fe(η(5)-C5H4COMe)Cp][BF4] as well as the subsequent reduction of the corresponding product [5][BF4] with decamethylferrocene (Fc*) each proceeded in greater than 95% yield. Mössbauer, UV/Vis and EPR spectroscopy analysis confirmed that [5][BF4] contained a ferrocenium species, indicating that the iron center was selectively oxidized over the ruthenium center. Complexes 5 and [5][BF4] were found to catalyze the ring-closing metathesis (RCM) of diethyl diallylmalonate with observed pseudo-first-order rate constants (k(obs)) of 3.1×10(-4) and 1.2×10(-5) s(-1), respectively. By adding suitable oxidants or reductants over the course of a RCM reaction, complex 5 was switched between different states of catalytic activity. A second-generation N-heterocyclic carbene that featured a 1',2',3',4',5'- pentamethylferrocenyl moiety (10) was also prepared and metal complexes containing this ligand were found to undergo iron-centered oxidations at lower potentials than analogous complexes supported by 2 (0.30-0.36 V vs. 0.56-0.62 V, respectively). Redox switching experiments using [Ru(10)Cl2(=CH-o-O-iPrC6H4)] revealed that greater than 94% of the initial catalytic activity was restored after an oxidation-reduction cycle.

A new ferrocene derivative blocks KRAS localization and function by oxidative modification at His95.

Ras proteins are membrane-bound GTPases that regulate essential cellular processes at the plasma membrane (PM). Constitutively active mutations of K-Ras, one of the three Ras isoforms in mammalian cells, are frequently found in human cancers. Ferrocene derivatives, which elevate cellular reactive oxygen species (ROS), have shown to block the growth of non-small cell lung cancers (NSCLCs) harboring oncogenic mutant K-Ras. Here, we developed and tested a novel ferrocene derivative on the growth of human pancreatic ductal adenocarcinoma (PDAC) and NSCLC. Our compound inhibited the growth of K-Ras-dependent PDAC and NSCLC and abrogated the PM binding and signaling of K-Ras, but not other Ras isoforms. These effects were reversed upon antioxidant supplementation, suggesting a ROS-mediated mechanism. We further identified K-Ras His95 residue in the G-domain as being involved in the ferrocene-induced K-Ras PM dissociation via oxidative modification. Together, our studies demonstrate that the redox system directly regulates K-Ras PM binding and signaling via oxidative modification at the His95, and proposes a role of oncogenic mutant K-Ras in the recently described antioxidant-induced metastasis in K-Ras-driven lung cancers.

A new ferrocene derivative blocks K-Ras localization and function by oxidative modification at His95.

Ras proteins are membrane-bound GTPases that regulate essential cellular processes at the plasma membrane (PM). Constitutively active mutations of K-Ras, one of the three Ras isoforms in mammalian cells, are frequently found in human cancers. Ferrocene derivatives, which elevate cellular reactive oxygen species (ROS), have shown to block the growth of non-small cell lung cancers harboring oncogenic mutant K-Ras. Here, we tested a novel ferrocene derivative on the growth of pancreatic ductal adenocarcinoma and non-small cell lung cancer. Our compound, which elevated cellular ROS levels, inhibited the growth of K-Ras-driven cancers, and abrogated the PM binding and signaling of K-Ras in an isoform-specific manner. These effects were reversed upon antioxidant supplementation, suggesting a ROS-mediated mechanism. We further identified that K-Ras His95 residue plays an important role in this process, and it is putatively oxidized by cellular ROS. Together, our study demonstrates that the redox system directly regulates K-Ras/PM binding and signaling via oxidative modification at the His95, and proposes a role of oncogenic mutant K-Ras in the recently described antioxidant-induced growth and metastasis of K-Ras-driven cancers.

Detailed structural and spectroscopic elucidation of ferrocenium coupled N-heterocyclic carbene gold(I) complexes.

Unambiguous assignment of redox sites on ferrocene coupled N-heterocyclic carbene gold(I) complexes [(Fc-NHC)2Au(I)]+ is critical to gain a greater mechanistic understanding of their activity in a cellular environment. Such information can be garnered with isolation and detailed characterization of the oxidized version of [(Fc-NHC)2Au(I)]+. Herein we disclose a study that unambiguously illustrates redox events pertaining to [(Fc-NHC)2Au(I)]+ that stem exclusively from ferrocene sites. This work also describes novel synthetic methodologies for isolating ferrocenium coupled N-heterocyclic carbene gold(I) complexes.

Long-range spin coupling: a tetraphosphine-bridged palladium dimer.

The dipalladium compound [{(adt)Pd}(2)(µ-tpbz)] (1) (adt = bis(p-anisyl)-1,2-ethylenedithiolate, tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene) has been synthesized from [{Cl(2)Pd}(2)(µ-tpbz)] by transmetalation employing (adt)SnMe(2). The cyclic voltammogram (CV) of 1 reveals reversible oxidation waves at 0.00 V and +0.50 V (vs [Fc](+)/Fc) with current amplitude twice that for identical processes in the monopalladium compound [(adt)Pd(dppb)] (2) (dppb = 1,2-bis(diphenylphosphino)benzene), an observation indicating each wave involves simultaneous one-electron oxidations at each metallodithiolene fragment. This assignment is affirmed by density functional theory (DFT) calculations that show the redox-active molecular orbital (MO) is principally composed of the dithiolene S(2)C(2) π-system, and by spectroelectrochemical UV-vis of [1](2+), which displays hallmark low energy charge transfer (CT) bands. Dication [1](2+) is a diradical with a near degenerate singlet-triplet ground state; fluid solution electron paramagnetic resonance (EPR) spectra validate the DFT-derived isotropic exchange coupling, J' = -6.3 cm(-1). The frozen solution X-band EPR spectrum of [1](2+) is consistent with a spin-triplet bearing a very faint half-field ("ΔM(S) = 2") signal. It is successfully simulated with an amazingly small zero field splitting, D = -15 × 10(-4) cm(-1) and negligible rhombicity (E/D = 0.008). These zero-field splitting parameters, which stem from the long-range dipolar spin coupling, are very accurately reproduced using a multipoint dipole model with an optimized interspin distance of 12.434 Å. With the framework reported herein for understanding how the weak interaction of two spins is mediated by tpbz, this bridging ligand can now be incorporated into extended systems with tailored chemical and physical properties for use in a variety of molecular-based electronic and magnetic devices.

The dithiolene ligand and tetrathiafulvalene precursor molecules 4,5-bis(bromomethyl)-1,3-dithiol-2-one and 4,5-bis[(dihydroxyphosphoryl)methyl]-1,3-dithiol-2-one.

The crystal structures of 4,5-bis(bromomethyl)-1,3-dithiol-2-one, C(5)H(4)Br(2)OS(2), (I), and 4,5-bis[(dihydroxyphosphoryl)methyl]-1,3-dithiol-2-one, C(5)H(8)O(7)P(2)S(2), (II), occur with similar unit cells in the same monoclinic space group. Both molecules reside on a twofold symmetry axis coincident with the C=O bond, so that the substituents in the 4- and 5-positions project above and below the plane of the 1,3-dithiol-2-one ring. In both structures, the molecules align themselves in a head-to-tail fashion along the b axis, and these rows of molecules then stack, with alternating directionality, along the c axis. For (II), an extensive network of intermolecular hydrogen bonds occurs between molecules within the same stack and between adjacent stacks. Each -CH(2)P(O)(OH)(2) group participates in four hydrogen bonds, twice as donor and twice as acceptor.

Synthesis, structures, and properties of 1,2,4,5-benzenetetrathiolate linked group 10 metal complexes.

Dimetallic compounds [(P-P)M(S(2)C(6)H(2)S(2))M(P-P)] (M = Ni, Pd; P-P = chelating bis(phosphine), 3a-3f) are prepared from O=CS(2)C(6)H(2)S(2)C=O or (n)Bu(2)SnS(2)C(6)H(2)S(2)Sn(n)Bu(2), which are protected forms of 1,2,4,5-benzenetetrathiolate. Selective monodeprotections of O=CS(2)C(6)H(2)S(2)C=O or (n)Bu(2)SnS(2)C(6)H(2)S(2)Sn(n)Bu(2) lead to [(P-P)Ni(S(2)C(6)H(2)S(2)C=O)] or [(P-P)Ni(S(2)C(6)H(2)S(2)Sn(n)Bu(2))]; the former is used to prepare trimetallic compounds [(dcpe)Ni(S(2)C(6)H(2)S(2))M(S(2)C(6)H(2)S(2))Ni(dcpe)] (M = Ni (6a) or Pt (6b); dcpe = 1,2-bis(dicyclohexylphosphino)ethane). Compounds 3a-3f are redox active and display two oxidation processes, of which the first is generally reversible. Dinickel compound [(dcpe)Ni(S(2)C(6)H(2)S(2))Ni(dcpe)] (3d) reveals two reversible oxidation waves with DeltaE(1/2) = 0.66 V, corresponding to K(c) of 1.6 x 10(11) for the mixed valence species. Electrochemical behavior is unstable to repeated scanning in the presence of [Bu(4)N][PF(6)] electrolyte but indefinitely stable with Na[BArF(24)] (BArF(24) = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), suggesting that the radical cation generated by oxidation is vulnerable to reaction with PF(6)(-). Chemical oxidation of 3d with [Cp(2)Fe][BArF(24)] leads to formation of [3d][BArF(24)]. Structural identification of [3d][BArF(24)] reveals appreciable shortening and lengthening of C-S and C-C bond distances, respectively, within the tetrathioarene fragment compared to charge-neutral 3d, indicating this to be the redox active moiety. Attempted oxidation of [(dppb)Ni(S(2)C(6)H(2)S(2))Ni(dppb)] (3c) (dppb = 1,2-bis(diphenylphosphino)benzene) with AgBArF(24) produces [[(dppb)Ni(S(2)C(6)H(2)S(2))Ni(dppb)](2)(mu-Ag(2))][BArF(24)](2), [4c][BArF(24)](2), in which no redox chemistry has occurred. Crystal structures of bis(disulfide)-linked compounds [(P-P)Ni(S(2)C(6)H(2)(mu-S(2))(2)C(6)H(2)S(2))Ni(P-P)] are reported. Near IR spectroscopy upon cationic [3d](+) and neutral 6a reveals multiple intense absorptions in the 950-1400 nm region. Time-dependent density functional theory (DFT) calculations on a 6a model compound indicate that these absorptions are transitions between ligand-based pi-type orbitals that have significant contributions from the sulfur p orbitals.

Synthesis, structures, and properties of mixed dithiolene-carbonyl and dithiolene-phosphine complexes of tungsten.

A new, high yield synthesis of [Ni(S(2)C(2)Me(2))(2)] (3) is described using 4,5-dimethyl-1,3-dithiol-2-one, Me(2)C(2)S(2)CO (1), as dithiolene ligand precursor. Reaction of (Me(2)C(2)S(2))Sn(n)Bu(2), 2, with WCl(6) produces tris(dithiolene) [W(S(2)C(2)Me(2))(3)] (6) and demonstrates the potential synthetic utility of this compound in metallodithiolene synthesis. The series of compounds [W(S(2)C(2)Me(2))(x)(CO)(6-2x)] (x = 1-3), obtained as a mixture via the reaction of [Ni(S(2)C(2)Me(2))(2)] with [W(MeCN)(3)(CO)(3)], has been characterized structurally. A trigonal prismatic geometry is observed for [W(S(2)C(2)Me(2))(CO)(4)] (4) and confirmed by a DFT geometry optimization to be lower in energy than an octahedron by 5.1 kcal/mol. The tris(dithiolene) compound [W(S(2)C(2)Me(2))(3)] crystallizes in disordered fashion upon a 2-fold axis in C2/c, a different space group than that observed for its molybdenum homologue (P1), which is attributed to a slightly smaller chelate fold angle, alpha, in the former. The reactivity of 4 and [W(S(2)C(2)Me(2))(2)(CO)(2)] (5) toward PMe(3) has been examined. Compound 4 yields only [W(S(2)C(2)Me(2))(CO)(2)(PMe(3))(2)] (7), while 5 produces either [W(S(2)C(2)Me(2))(2)(CO)(PMe(3))] (8) or [W(S(2)C(2)Me(2))(2)(PMe(3))(2)] (9) depending upon reaction conditions. Crystallographic characterization of 5, 8, and 9 reveals a trend toward greater reduction of the dithiolene ligand (i.e., more ene-1,2-dithiolate character) across the series, as manifested by C-C and C-S bond lengths. These structural data indicate a profound effect exerted by the pi-acidic CO ligands upon the apparent state of reduction of the dithiolene ligand in compounds with ostensibly the same oxidation state.

Synthesis and molecular structure of biologically significant bis(1,3-dimesityl-4,5-naphthoquinoimidazol-2-ylidene)gold(I) complexes with chloride and dichloridoaurate counter-ions.

Diffraction-quality single crystals of two gold(I) complexes, namely bis(1,3-dimesityl-4,5-naphthoquinoimidazol-2-ylidene)gold(I) chloride benzene monosolvate, [Au(C29H26N2O2)2]Cl·C6H6 or [(NQMes)2Au]Cl·C6H6, 2, and bis(1,3-dimesityl-4,5-naphthoquinoimidazol-2-ylidene)gold(I) dichloridoaurate(I) dichloromethane disolvate, [Au(C29H26N2O2)2][AuCl2]·2CH2Cl2 or [(NQMes)2Au][AuCl2]·2CH2Cl2, 4, were isolated and studied with the aid of single-crystal X-ray diffraction analysis. Compound 2 crystallizes in a monoclinic space group C2/c with eight molecules in the unit cell, while compound 4 crystallizes in the triclinic space group P-1 with two molecules in the unit cell. The crystal lattice of compound 2 reveals C-H...Cl- interactions that are present throughout the entire structure representing head-to-tail contacts between the aromatic (C-H) hydrogens of naphthoquinone and Cl- counter-ions. Compound 4 stacks with the aid of short interactions between a naphthoquinone O atom of one molecule and the mesityl methyl group of another molecule along the a axis, leading to a one-dimensional strand that is held together by strong π-η2 interactions between the imidazolium backbone and the [AuCl2]- counter-ion. The bond angles defined by the AuI atom and two carbene C atoms [C(carbene)-Au-C(carbene)] in compounds 2 and 4 are nearly rectilinear, with an average value of ∼174.1 [2]°. Though 2 and 4 share the same cation, they differ in their counter-anion, which alters the crystal lattice of the two compounds. The knowledge gleaned from these studies is expected to be useful in understanding the molecular interactions of 2 and 4 under physiological conditions.

Di-µ-acetato-bis{[3-benzyl-1-(2,4,6-trimethylphenyl)imidazol-2-ylidene]silver(I)}.

The title compound, [Ag2(C2H3O2)2(C19H20N2)2] (2), was readily synthesized by treatment of 3-benzyl-1-(2,4,6-trimethylphenyl)imidazolium chloride with silver acetate. The solution structure of the complex was analyzed by NMR spectroscopy, while the solid-state structure was confirmed by single-crystal X-ray diffraction studies. Compound 2 crystallizes in the triclinic space group P1¯, with a silver-to-carbene bond length (Ag-CNHC) of 2.084 (3) Å. The molecule resides on an inversion center, so that only half of the molecule is crystallographically unique. The planes defined by the two imidazole rings are parallel to each other, but not coplanar [interplanar distance is 0.662 (19) Å]. The dihedral angles between the imidazole ring and the benzyl and mesityl rings are 77.87 (12) and 72.86 (11)°, respectively. The crystal structure features π-π stacking interactions between the benzylic groups of inversion-related (-x + 1, -y + 1, -z + 1) molecules and C-H ⋯ π interactions.

Expanding the biological utility of bis-NHC gold(i) complexes through post synthetic carbamate conjugation.

We report the synthesis of a novel hydroxyl-functionalised heteroleptic bis-NHC gold(i) complex that permits conjugation to various amines via carbamate bond formation. The resulting derivatives were studied in vitro using cell proliferation assays and fluorescent microscopic imaging of human cancer cell lines.

A convergent approach to the synthesis of multimetallic dithiolene complexes.

Controlled base hydrolysis of one or both of the protected 1,2-dithiolene chelates of 1,3,5,7-tetrathia- s-indacene-2,6-dione (OCS 2C 6H 2S 2CO) enables the stepwise synthesis of di- and trimetallic complexes with 1,2,4,5-benzenetetrathiolate as the connector. Treatment of OCS 2C 6H 2S 2CO with MeO (-), followed by [NiBr 2(dcpe)] [dcpe = 1,2-bis(dicyclohexylphosphino)ethane], yields [(dcpe)Ni(S 2C 6H 2S 2CO)] ( 4). The reaction of 4 with EtO (-), followed by [MX 2(dcpe)] (X = halide), yields [(dcpe)Ni(S 2C 6H 2S 2)M(dcpe)] [M = Ni ( 5a), Pd ( 5b)]. Deprotection of the 1,3-dithiol-2-one group of 4, followed by introduction of (1)/ 2 equiv of MX 2 and then I 2, yields the neutral trimetallic compounds [(dcpe)Ni(S 2C 6H 2S 2)] 2M [M = Ni ( 6a), Pt ( 6b)]. Tetrahedralization at nickel is observed in 5a, which density functional theory calculations attribute to second-order Jahn-Teller effects, while 6a and 6b display an end-to-end folding of approximately 46 degrees . A color darkening is observed in moving from 4 to compounds 6 due to the increasing size of the conjugated metal-organic pi system. Intense, broad absorptions in the near-IR are observed for 6a and 6b.

Structurally Characterized Cationic Silver(I) and Ruthenium(II)carbene complexes of 1,2,3-Triazol-5-ylidenes.

A novel 1,3,4-substituted 1,2,3-triazolium salt was found to function as an effective precursor for the synthesis of the first structurally characterized cationic silver(I) and ruthenium(II)carbene complexes of overall 1:2 ligand-to-metal stoichiometry. The Ag(I) complex crystallized in the form of an eight silver atom-containing cluster, whereas the Ru(II) complex proved to be a discrete species and was found to be capable of initiating the ring-opening metathesis polymerization of norbornene upon activation with (trimethylsilyl)diazomethane.

Preparation and isolation of dithiolene thiophosphoryl molecules as stable, protected forms of dithiolene ligands.

The reaction of P4S10 with acyloins, RC(O)CH(OH)R, in refluxing dioxane, followed by the addition of alkylating agents, forms dithiolene thiophosphoryl thiolate compounds, (R2C2S2)P(S)(SR'), which are readily isolated and purified. The compounds that have been prepared and identified spectroscopically are those with R = p-anisyl, R' = Me (1); R = p-anisyl, R' = Bz (2); R = Ph, R' = Me (4); R = Et, R' = Bz (5). Compounds 1, 2, and 4 were structurally characterized by X-ray crystallography and found to possess a tetrahedral coordination geometry about the phosphorus atom, with overall Cs symmetry. In each case, the mirror plane bisects the dithiolene S-P-S chelate and contains the thiophosphoryl bond, which ranges in length from 1.9241(8) to 1.9361(7) A. The use of 2-(bromomethyl)naphthalene as organic electrophile in the P4S10/acyloin reaction produced bis(2-methylnaphthalenyl) disulfide as the only identifiable product. The substitution of Lawesson's reagent for P4S10 in reactions with acyloins produced deoxy acyloin rather than products resulting from chalcogen exchange. Compounds 1-2 and 4-5 are Group 5 analogues of 1,3-dithiol-2-ones, (R2C2S2)C=O, and undergo a similar hydrolysis in aqueous base to liberate ene-1,2-dithiolate dianions from which corresponding metal dithiolene complexes may be prepared. Deprotection of 1 in MeO-/MeOH, followed by the addition of NiCl2.6H2O and then I2, produces square planar [Ni(S2C2(C6H4-p-OCH3)2)2] (8) in 93% yield. A high-resolution structure of 8 (P) reveals dithiolene C-C and C-S bond lengths that are clearly indicative of the thionyl radical monoanionic nature of the ligand. The use of isolated (R2C2S2)P(S)(SR') compounds as a dithiolene ligand source for the preparation of metal dithiolene complexes offers the advantages of clean reactivity and high yield.

Reversible, electrochemically controlled binding of phosphine to iron and cobalt bis(dithiolene) complexes.

The homoleptic bis(dithiolene) complexes [M(S(2)C(2)R(2))(2)](2) (M = Fe, Co; R = p-anisyl) undergo two successive reductions to form anions that display [M(S(2)C(2)R(2))(2)](2)(2-) <--> 2[M(S(2)C(2)R(2))(2)](1-) solution equilibria. The neutral dimers react with Ph3P to form square pyramidal [M(Ph(3)P)(S(2)C(2)R(2))(2)](0). Voltammetric measurements upon [M(Ph(3)P)(S(2)C(2)R(2))(2)](0) in CH(2)Cl(2) reveal only irreversible features at negative potentials, consistent with Ph(3)P dissociation upon reduction. Dissociation and reassociation of Ph(3)P from and to [Fe(Ph(3)P)(S(2)C(2)R(2))(2)](0) is demonstrated by spectroelectrochemical measurements. These collective observations form the basis for a cycle of reversible, electrochemically controlled binding of Ph(3)P to [M(S(2)C(2)R(2))(2)](2) (M = Fe, Co; R = p-anisyl). All members of the cycle ([M(S(2)C(2)R(2))(2)](2)(0), [M(S(2)C(2)R(2))(2)](2)(1-), [MM(S(2)C(2)R(2))(2)](2)(2-), [M(S(2)C(2)R(2))(2)](1-), [M(Ph(3)P)(S(2)C(2)R(2))(2)]) for M = Fe, Co have been characterized by crystallography. Square planar [Fe(S(2)C(2)R(2))(2)](1-) is the first such iron dithiolene species to be structurally identified and reveals Fe-S bond distances of 2.172(1) and 2.179(1) Angstrom, which are appreciably shorter than those in corresponding square planar dianions.