Arnold Rheingold

• PhD
• Professor at University of California, San Diego

Seven magnesium complexes (1–7) were synthesized by reaction of new (L³‐H–L⁵‐H) and previously reported ketoimine pro‐ligands with dibutyl magnesium and were isolated in 59–70% yields. Complexes 1–7 were characterized fully and consisted of bis‐ligated homoleptic ketoiminates coordinated in distorted octahedral geometry around the magnesium centers...

Previously, ferrocene incorporation into the principal structural component of biologically active molecules resulted in enhanced cytotoxic activity against hormone-dependent MCF-7 and T-47D and hormone-independent MDA-MB-231 breast-cancer cell lines. Here we explore 4 new ferrocene estrogen conjugates at position 16 of the estrogen hormone and com...

Elemental white phosphorus (P4) is well recognized as a critical precursor to organophosphorus compounds. However, regulatory constraints stemming from the toxic and pyrophoric nature of white phosphorus have significantly limited its accessibility. Herein is described a new approach to white phosphorus storage and release based on a unique example...

Carboranes are boron-rich molecular clusters possessing electronic characteristics that allow for orthogonal approaches to vertex-selective modifications. We report improved functionalization methods utilizing orthogonal chemistry to achieve efficient substitution at electron-rich B-vertices and electron-poor C-vertices of carborane. Functionalizat...

Elemental white phosphorus (P4) is well recognized as a critical precursor to organophosphorus compounds. However, regulatory constraints stemming from the toxic and pyrophoric nature of white phosphorus have significantly limited its accessibility. Herein is described a new approach to white phosphorus storage and release based on a unique example...

table> We report improved methods utilizing orthogonal chemistry to achieve efficient substitution at electron-rich B-vertices and electron-poor C-vertices of carborane. Functionalization of B-vertices with alkyl and (hetero)aryl groups using corresponding Grignard reagents has been improved by the use of a Pd-based precatalyst featuring an electr...

Oxidation of distorted square-planar perfluoropinacolate Co compound [Co II (pin F ) 2 ] ²⁻ , 1 , to [Co III (pin F ) 2 ] ¹⁻ , 2 , is reported.

A synthetic strategy conceived with the intent of establishing a novel approach to the de novo construction of ryanoids is described that is based on a recently developed metallacycle-mediated intramolecular oxidative alkyne–1,3-diketone coupling reaction. In short, a one-pot annulation/oxidation sequence is shown to be capable of establishing a de...

[Y(N(SiMe3)2)3] reacts with (Ad,MeArOH)3mes to form the Y3+ complex [((Ad,MeArO)3mes)Y], 1-Y. This complex reacts with potassium metal in the presence of 2.2.2-cryptand to give a cocrystallized mixture of [K(2.2.2-cryptand)][((Ad,MeArO)3mes)Y], 2-Y, and [K(2.2.2-cryptand)][((Ad,MeArO)3mes)YH], 3-Y. The electron paramagnetic resonance spectrum of th...

We report the synthesis of two isomeric Pt(II) complexes ligated by doubly deprotonated 1,1′-bis(o-carborane) (bc). The κ²-C,C-bound isomer (3a) is generated through salt metathesis of K2[bc] and Pt(dtb-bpy)Cl2 (dtb-bpy = 4,4′-di-tert-butyl-2,2′-bipyridine), whereas the κ²-B,C-bound isomer (3b) forms after the addition of K[H-bc] to a reaction mixt...

The strong π‐acidity of the twelve CO ligands of [Fe4(μ4‐N)(CO)12]⁻ reduces the reactivity of the interstitial nitrogen atom. In their Communication (DOI: 10.1002/anie.201801206), J. S. Figueroa and co‐workers show that replacing four of the CO ligands with electron‐donating m‐terphenyl isocyanides (turbine generators) activates the nucleophilicity...

Aufgrund der starken π‐Acidität der zwölf CO‐Liganden in [Fe4(μ4‐N)(CO)12]⁻ ist das interstitielle Nitrid nicht reaktiv. In ihrer Zuschrift (DOI: 10.1002/ange.201801206) zeigen J. S. Figueroa et al., dass durch den Austausch von vier CO‐Liganden durch elektronenschiebende m‐Terphenylisocyanide (Turbinen) das Nitrid zum reaktiven Nucleophil wird (Gl...

Oxidative addition of methylene chloride to Pd((R,R)-Me-DuPhos)(L) (1–3; L = P(t-Bu)3, PCy3, or trans-stilbene) gave Pd((R,R)-Me-DuPhos)(CH2Cl)(Cl) (4). Treatment of [Rh(COD)(Cl)]2 with (R,R)-Me-DuPhos at low temperature in THF or CH2Cl2 afforded [Rh((R,R)-Me-DuPhos)(Cl)]2 (5). At room temperature, these reactions also gave the byproduct [Rh((R,R)-...

Turn on ESIPT based chemosensor for histidine: Application in urine analysis and live cell imaging

Generating monovalent pnictogens within NCN pincers has resulted in the isolation of three distinct types of 1,2-azaheteroles, highly aromatic nitrogen analogues like pyrazole-based 5, aromatic yet fluxional P- and As-derived bell-clappers 1 and 2, and hypervalent Sb and Bi derivatives 3 and 4, which are supported by 3-center, 4-electron N–E–N bond...

The design of molecular complexes of earth-abundant first-row transition metals that can catalyze multi-electron C–H bond activation processes is of interest for achieving efficient, low-cost syntheses of target molecules. To overcome the propensity of these metals to perform single-electron processes, redox-active ligands have been utilized to pro...

We report solid‐state nuclear magnetic resonance ¹H spin‐lattice relaxation, single‐crystal X‐ray diffraction, powder X‐ray diffraction, field emission scanning electron microscopy, and differential scanning calorimetry in solid samples of 2‐ethylanthracene (EA) and 2‐ethylanthraquinone (EAQ) that have been physically purified in different ways fro...

A known ligand precursor, prepared by an improved method from 1,3-bis(bromomethylbenzene), a base, and (R,R)-2,5-dimethylphospholane-borane, was deprotected with DABCO and used to prepare chiral m-xylene-based PCP pincer complexes. Reaction with Ni(DME)Br2 and NEt3 gave square planar Ni(DuPinPhos)(Br) (9), which was crystallographically characteriz...

Reported here is the isolation of a dianionic cobalt terminal carbyne derived from chemical reduction of an encumbering isocyanide ligand. Crystallographic, spectroscopic and computational data reveal that this carbyne possesses a low-valent cobalt center with an extensively-filled d-orbital manifold. This electronic character renders the cobalt ce...

Alkylation of 4-methoxy-1H-pyrazolo[3,4-d]pyrimidine (1b) with iodomethane in THF using NaHMDS as base selectively provided N2-methyl product 4-methoxy-2-methyl-2H-pyrazolo[3,4-d]pyrimidine (3b) in 8/1 ratio over N1-methyl product (2b). Interestingly, conducting the reaction in DMSO reversed selectivity to provide a 4/1 ratio of N1/N2 methylated pr...

Tandem alkylation/arylation of primary phosphines PH2R (R = Ph, Cy, Fc, FcCH2; Fc = ferrocenyl) with 5-bromo-6-chloromethylacenaphthene (1) and 2 equiv of NaOSiMe3 using the catalyst precursor Cu(IPr)(Cl) gave a series of 1-phosphapyracenes (R-PyraPhos, 2a–d), which were isolated as borane adducts 3a–d. Similar reactions of the chiral air-stable pr...

An efficient method for chemoselective cysteine arylation of unprotected peptides and proteins using Au(III) organometallic complexes is reported. The bioconjugation reactions proceed rapidly (<5 min) at ambient temperature in various buffers and within a wide pH range (0.5-14). This approach provides access to a diverse array of S-aryl bioconjugat...

We report a new class of redox-active vertex-differentiated dodecaborate clusters featuring pentafluoroaryl groups. These [B12(OR)11NO2] clusters share several unique photophysical properties with their [B12(OR)12] analogues, while exhibiting significantly higher (+0.5 V) redox potentials. This work describes the synthesis, characterization, and is...

We report a cinchona alkaloid catalyzed addition of thiophenol into rapidly interconverting aryl-naphthoquinones, resulting in stable biaryl atropisomers upon reductive methylation. An array of thiophenols and naphthoquinone substrates were evaluated and we observed selectivities up to 98.5:1.5 e.r.. Control of the quinone redox properties allowed...

Multi‐metallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ4‐nitrido cluster, [Fe4(μ4‐N)(CO)12]‐, this analogy is largely limited due to the electron withdrawing effect of carbonyl ligands on the iron‐nitride core. Described here is the synthesis and reactivity of [Fe4(μ4‐N)...

Multi‐metallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ4‐nitrido cluster, [Fe4(μ4‐N)(CO)12]‐, this analogy is largely limited due to the electron withdrawing effect of carbonyl ligands on the iron‐nitride core. Described here is the synthesis and reactivity of [Fe4(μ4‐N)...

Reaction of the enantiomerically enriched P-stereogenic phosphiranes syn-(RP,SC)-Mes*PCH2CH(Ph) (syn-1) and anti-(SP,SC)-Mes*PCH2CH(Ph) (anti-2, Mes* = 2,4,6-(t-Bu)3C6H2) with metal complex precursors gave Au(L)(Cl) (L = 1 (3); L = 2 (4)), trans-ML2Cl2 (L = 1, M = Pd (5), Pt (6)), Pd(η³-C3H5)(L)(Cl) (L = 1 (7)), and trans-RhL2(CO)(Cl) (L = 1 (8); L...

Regioselective formation of (E)‐β‐vinylstannanes has been a long‐standing challenge in transition‐metal‐catalyzed alkyne hydrostannation. Here we report a well‐defined molybdenum‐based system featuring two encumbering m‐terphenyl isocyanides that reliably and efficiently delivers high regioselectivity for (E)‐β‐vinylstannanes from a range of termin...

The synthesis and reactivity of a molecular nickel (II) complex 1 with the polypyridyl ligand framework N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine under electrochemically reducing conditions in the presence of CO2 is reported. Cyclic voltammetry, infrared spectroelectrochemistry (IR-SEC) and electrolysis experiments suggest this Ni complex...

Cisplatin and other metal-based drugs often display side effects and tumor resistance after prolonged use. Because rhenium-based anticancer complexes are often less toxic, a novel series of organorhenium complexes were synthesized of the types: XRe(CO)3Z (X = α-diimines and Z = p-toluenesulfonate, 1-naphthalenesulfonate, 2-naphthalenesulfonate, pic...

A quantitative assessment of the substituent, hybridization, and crystal-packing effects on the electronic, structural, and vibrational properties of halogen bonded systems is presented. Through a combined experimental and theoretical approach employing Raman spectroscopy, X-ray crystallography, and density functional theory (DFT), a series of soli...

Seven aluminum ion-pair complexes (1-7) were synthesized by reaction of NNO Schiff base ketoimines with differing substituents with tris(2,6-dimethylphenoxy) aluminum dimer in an inert atmosphere glovebox at room temperature. The complexes were characterized with ¹H, ¹³C, and ¹⁹F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, and...

Nucleophilic substitution results in inversion of configuration at the electrophilic carbon (SN2) or racemization (SN1). Stereochemistry at the nucleophile is rarely considered, but phosphines, which have a high barrier to pyramidal inversion, attack electrophiles with retention of configuration at P. Surprisingly, cyclization of bifunctional secon...

Nucleophilic substitution results in inversion of configuration at the electrophilic carbon (SN2) or racemization (SN1). Stereochemistry at the nucleophile is rarely considered, but phosphines, which have a high barrier to pyramidal inversion, attack electrophiles with retention of configuration at P. Surprisingly, cyclization of bifunctional secon...

Protic NHC (PNHC) complexes with N¹H, N²-alkyl/aryl imidazolylidene ligands are relatively rare, and routes for their synthesis differ from what is used to make non-protic analogs. Prior work from our group and others showed that in the presence of a tethering ligand (phosphine or in one case, pyridine), CpM and Cp*M (M = Ir, Ru) PNHC complexes cou...

We report the synthesis of air-stable Pd(I) dimer complexes featuring biaryl phosphine ligands. Catalytic experiments suggest that these complexes are comptent precatalysts that can mediate cross-coupling amination reactions between aryl...

A family of magnesium and calcium salen-derivatives was synthesized and characterized for use as subterranean fluid flow monitors. For the Mg complexes, di-n-butyl magnesium ([Mg(Bun)2]) was reacted with N,N'-ethylene bis(salicylideneimine) (H2-salen), N,N'-bis(salicylidene)-1,2-phenylenediamine (H2-saloPh), N,N'-bis(3,5-di-t-butylsalicylidene)-eth...

Regioselective formation of (E)‐β‐vinylstannanes has been a long‐standing challenge in transition‐metal‐catalyzed alkyne hydrostannation. Here we report a well‐defined molybdenum‐based system featuring two encumbering m‐terphenyl isocyanides that reliably and efficiently delivers high regioselectivity for (E)‐β‐vinylstannanes from a range of termin...

Electrocatalytic energy conversion with molecular f-element catalysts is still in an early phase of its development. We here report detailed electrochemical investigations on the recently reported trivalent lanthanide coordination complexes [(Ad,MeArO)3mes)Ln] (1–Ln), with Ln = La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, that were now found to perform as a...

The reaction of TPypA (tris(2-pyridylmethyl)amine) and Fe(BF4)2 and sodium nitraniIate (Na21NO2) or Mn(O2CMe)2 with chloranilic acid (H21Cl) respectively forms [FeIII(TPyA)1NO2]2O and MnII(TPyA)1Cl, respectively. The structures of these 7-coordinate compounds have been determined. The former is a dinuclear FeIII compound possessing equivalent Fe(II...

We report a new class of redox-­‐active vertex-­‐differentiated dodecaborate clusters featuring pentafluoroaryl groups. These [B12(OR)11NO2] clusters share several unique photophysical properties with their [B12(OR)12] analogues, while exhibiting significantly higher (+0.5 V) redox potentials. This work describes the synthesis, characterization, an...

We report a new class of redox-­‐active vertex-­‐differentiated dodecaborate clusters featuring pentafluoroaryl groups. These [B12(OR)11NO2] clusters share several unique photophysical properties with their [B12(OR)12] analogues, while exhibiting significantly higher (+0.5 V) redox potentials. This work describes the synthesis, characterization, an...

We report the synthesis of two isomeric Pt(II) complexes ligated by doubly deprotonated 1,1′-bis( o -carborane) ( bc ). This work provides a potential route to fine-tune the electronic properties of luminescent metal complexes by virtue of vertex-differentiated coordination chemistry of carborane-based ligands.

H-bonding interaction of acidic moieties (CH2OH, COOH) at the 5- and 5’-positions of bis(1,3-phenylene)-32-crown-10 (1) with di- or tri-topic anions leads to enhanced formation of inclusion complexes with N,N’-dialkyl-4,4’-bipyridinium salts (“paraquats”, 2); the enforced folding of the crown ethers into pseudocryptands thus leads to pseudo-pseudor...

The reaction of magnesium chloride with two equivalents of sodium phosphaethynolate, Na[OCP]•(dioxane) 2.5 (1), yields a magnesium diphosphaethynolate complex, [(THF) 4 Mg(OCP) 2 ] (3). The formation of compound 3 goes through a monosubstituted chloromagnesium...

The synthesis and electrocatalytic reduction of dioxygen by a molecular manganese (III) complex with a tetradentate dianionic bipyridine-based ligand is reported. Electrochemical characterization suggests that upon reduction to Mn(II), the coordinated phenolate moieties of the ligand are protonated with a Nernstian dependence on the added proton so...

A permanently porous, three-dimensional metal-organic material formed from zero-valent metal nodes is presented. Combination of ditopic m-terphenyl diisocyanide, [CNArMes2]2, and the d10 Ni(0) precursor Ni(COD)2, produces a porous metal-organic material featuring tetrahedral [Ni(CNArMes2)4]n structural sites. X-ray absorption spectroscopy provides...

The bis-phenoxo-bridged dinuclear iron(III) compound Fe2(BBPA)2F2 (H2BBPA = N,N-bis(2-hydroxybenzyl)-N-(2-pyridylmethyl)amine) was structurally and magnetically characterized. It has distorted octahedral iron(III) centers with each iron(III) site having two cis-Fe(BBPA)F fragments that are bridged by two μ-phenoxo oxygen atoms. The dinuclear compou...

The reaction of chloroimidazolium chloride salt, [NHC-Cl][Cl], NHC = :C{N(2,6-iPr2C6H3)CH}2 (1) with two equivalents of sodium phosphaethynolate, Na[OCP]•(dioxane)2.5, results in the formation of highly reactive NHC adducts of diphosphorus and carbon monoxide, NHC-{cyclo-(CO)-P2-C(O)} (2) and NHC-P2-C(O)-NHC (3). Notably, in the presence of free NH...

For investigation of structure-property relationships in copper phosphine halide complexes, treatment of copper(I) halides with chiral bis(phosphines) gave dinuclear [Cu((R,R)-i-Pr-DuPhos)(μ-X)]2 [X = I (1), Br (2), Cl (3)], [Cu(μ-((R,R)-Me-FerroLANE)(μ-I)]2 (5), and [Cu((S,S)-Et-FerroTANE)(I)]2 (6), pentanuclear cluster Cu5I5((S,S)-Et-FerroTANE)3...

Photovoltaic Perovskites, most notably methylammonium lead triiodide, (NH3Me)PbI3, have recently attracted considerable attention, and based upon the 'Goldschmidt Tolerance Factor' hydrazinium should be able to occupy the same cation site as methylammonium. The reaction of N2H5+I- with PbI2 in DMF results in three types of yellow crystals; hexagona...

The Cover Feature shows a simple combination of a bis(o-carborane) and a magnesium source facilitating the synthesis of a Grignard-type bis(o-carborane) delivery system. The bis(o-carboranyl)magnesiate, which is an isolable powder and a solid that is stable under an inert atmosphere for months, functions to transfer the bis(o-carboranyl) ligand to...

Several high spin ground-state compounds based upon ferromagnetic coupling between a metal ion and the chelating 3,5-di-tert-butyl-1,2-semiquinonate radical anion, [DTBSQ]⁻, as they possess unpaired electron spins in orthogonal dx²−y²/dz² and π∗ orbitals, are described. [CuII(DPyA)(DTBSQ)](ClO4) (DPyA = 2,2′-dipyridylamine) was reinvestigated and i...

Controlling the isomerization of alkenes is important for the manufacturing of fuel additives, fine-chemicals and pharmaceuticals. But even if isomerization seems to be a simple unimolecular process, the factors that govern catalyst performance are far from clear. Here we present a set of models that describe selectivity and activity, enabling the...

Reaction of Ge2Ph6 (1) with trichloroacetic acid at 95°Cin toluene for 4 days yields a mixture of the two digermanes (Cl3CCOO)Ph2GeGePh2(OOCCCl3) (2) and Ph3GeGePh2(OOCCCl3) (3) that are converted to a mixture of ClPh2GeGePh2Cl (4) and Ph3GeGePh2Cl (5) using ethereal HCl. Treatment of the mixture of 4 and 5 with LiAlH4 affords the two digermanes HP...

The planned synthesis of hypervalent 10–P–3 and 10–As–3 compounds 1 and 2 from brominated bis(oxazoline) and bis(imine) NCN pincers via a lithiation/electrophilic quenching (with PnCl3; Pn = P or As)/reduction protocol resulted in unexpected findings and reactivity. Generation of bis(oxazoline)-ligated (NCN)PCl2 derivative CP resulted in an intramo...

2-R-1,3-Benzoxaphospholes (R-BOPs) are examples of fluorescent conjugated materials possessing low coordinate phosphorus centers. A series of 2-(p-XC6H4)-BOPs (X = H, Cl, Br, Me, OMe) react with [W(CO)5(NCMe)] to produce the crystalline complexes [W(CO)5(2-Ar-BOP)] (2a-e). All complexes were characterized by NMR spectroscopy and by single crystal X...

To develop Rh-catalyzed dehydrocoupling for stereocontrolled synthesis of P–P bonds, we prepared potential intermediates, chiral rhodium phosphine-phosphido complexes, and investigated their stoichiometric and catalytic transformations. Treatment of [Rh(diphos*)(COD)][X] with the bis(secondary phosphine) IsHPCH2PHIs (1, Is = 2,4,6-(i-Pr)3C6H2) gave...

Densely substituted and highly oxygenated carbocycles are challenging targets for synthesis. In particular, those possessing numerous contiguous, fully-substituted carbon atoms (i.e., tertiary alcohols and quaternary centers) are often not accessible in a direct fashion, necessitating the strategic decoupling of ring-formation from the establishmen...

Using solid state 1H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments, we have investigated the effects of several solid-solid phase transitions on t-butyl group and methyl group rotation in solid 1,3,5-tri-t-butylbenzene. The goal is to relate the dynamics of the t-butyl groups and their constituent methyl groups to properties...

Cp′ 2 Ln(THF) 2 metallocenes (Cp′ = C 5 H 4 SiMe 3 ) react with 2.2.2-cryptand (crypt) to form Ln ²⁺ -in-crypt complexes, [Ln(crypt)(THF)][Cp′ 3 Ln] 2 (Ln = Sm, Eu) and [Yb(crypt)][Cp' 3 Yb] 2 , that contain Ln ²⁺ ions surrounded only by neutral ligands. A...

The encumbered tetraisocyanide dianion, Na2[Fe(CNArMes2)4], reacts with two molecules of CO2 to effect reductive disproportionation to CO and carbonate ([CO3]2-). When the reaction is performed in the presence of silyl triflates, reductive disproportionation is arrested via silylative esterification of a mono-CO2 adduct. This results in the formati...

The encumbered tetraisocyanide dianion, Na2[Fe(CNArMes2)4], reacts with two molecules of CO2 to effect reductive disproportionation to CO and carbonate ([CO3]2-). When the reaction is performed in the presence of silyl triflates, reductive disproportionation is arrested via silylative esterification of a mono-CO2 adduct. This results in the formati...

The synthesis of two biscarboranyl (bc) magnesium reagents is described. Treatment of 1,1'-bis(o-carborane) (H2-bc) or 8,8',9,9',10,10',12,12'-octamethyl-1,1'-bis(o-carborane) (H2-Mebc) with Mg(n-Bu)2 in 1,2-dimethoxyethane (DME) affords (bc)Mg(DME)2 (1a-b) as crystalline solids. The magnesium compounds, which have been characterized by NMR spectro...

Several high spin ground-state compounds based upon ferromagnetic coupling between a metal ion and the chelating 3,5-di-tert-butyl-1,2-semiquinonate radical anion, [DTBSQ]•-, as they possess unpaired electron spins in orthogonal dx2-y2/dz2 and π∗ orbitals, are described. [CuII(DPyA)(DTBSQ)](ClO4) (DPyA = 2,2’-dipyridylamine) was reinvestigated and...

Four ferrocene-steroid conjugates (steroid = 3α-hydroxy androstan-17-one (androsterone, 3β-hydroxy androstan-17-one (trans-androsterone), 3β-hydroxy pregn-5-en-18-one (pregnenolone) and 3β-hydroxy dehydroandrostan-17-one (dehydroepiandrosterone, DHEA)) were synthesized and structurally characterized by analytical methods. The molecular structures o...

The dimeric bridging carbonyl complexes [(μ-CO)2[CpCo]2]ⁿ (n = 0, 1−) have occupied a central position in the understanding of metal–metal bonding interactions when bridging ligands are present. Based on simple electron-counting formalisms, these dimers have been proposed to possess formal Co–Co bond orders of 2 and 1.5, respectively. However, this...

We report the first observed Pd-catalyzed isomerization (cage-walking) of 9-bromo-meta-carborane during Pd-catalyzed cross-coupling which enables formation of B–O and B–N bonds at all boron vertices (B(2), B(4), B(5), and B(9)) of meta-carborane. Experimental and theoretical studies suggest this isomerization mechanism is strongly influenced by the...

While interest in cooperative reactivity of transition metals and Lewis acids is receiving significant attention, the scope of known reactions that directly exploit the polarized reverse-dative σ-bond of metal-borane complexes (i.e., M→BR3 ) remains limited. Described herein is that the platinum (boryl)iminomethane (BIM) complex [Pt(κ(2) -N,B-(Cy2)...

While interest in cooperative reactivity of transition metals and Lewis acids is receiving significant attention, the scope of known reactions that directly exploit the polarized reverse-dative σ-bond of metal-borane complexes (i.e., MBR3) remains limited. Described herein is that the platinum (boryl)iminomethane (BIM) complex [Pt(κ2-N,B-Cy2BIM)(CN...

Using the stable metalloradical Mn(CO)3(CNArDipp2)2, we report the formation of manganese-main group complexes via the single-electron functionalization of main group halides. The reactions occur in a simple 1:1 stochiometry, and demonstrate the utility of using stable open-shelled organometallics as precursors for metal-main group compounds. This...

Reaction of the zirconium–benzyne complex [Cp2Zr(PMe3)(C6H4)] with sodium phosphaethynolate, Na[OCP], affords a zircono-phosphaalkene complex. Notably, unlike reactions of other transition metal complexes with Na[OCP] that yield the products of simple salt metathesis, this transformation represents novel Na[OCP] insertion chemistry and formation of...

An efficienct copper-catalyzed direct arylation reaction for the regioselective functionalization of benzodithiophene-S,S-tetraoxide has been developed. The method demonstrates a broad scope with isolated yields ranging from good to excellent. Furthermore, the reaction specificity for aryl iodides over the unreactive aryl bromides provide a opportu...

The triiron trihydride complex Fe3H3L (1) [where L³⁻ is a tris(β-diketiminate)cyclophanate] reacts with CO and with BF3·OEt2 to afford (FeICO)2FeII(μ3-H)L (2) and Fe3F3L (3), respectively. Variable-temperature and applied-field Mössbauer spectroscopy support the assignment of two high-spin (HS) iron(I) centers and one HS iron(II) ion in 2. Prelimin...

Side-by-side: Two trinuclear copper-dioxygen species have been characterized by UV/Vis stopped-flow spectroscopy in solution—an asymmetric and a symmetric one being the final product of the oxygenation. For the first time, these rare biomimetic species could be stabilized by dianionic ligands by using perfluoropinacolate. The asymmetric trinuclear...

Correction for: ‘Synthesis, X-ray characterization, DFT calculations and Hirshfeld surface analysis of thiosemicarbazone complexes of Mⁿ⁺ ions (n = 2, 3; M = Ni, Cd, Mn, Co and Cu)’ by Ghodrat Mahmoudi et al., CrystEngComm, 2016, 18, 1009–1023.

The synthesis of fully alkylated closo-hexaborate dianions is reported. The reaction of [NBu4][B6H6Hfac], benzyl bromide, and triethylamine under microwave heating conditions affords persubstituted [NBu4][B6(CH2Ar)6Hfac] (Ar = C6H5, 4–Br-C6H4), which have been isolated and characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray d...

The recent Ebola virus (EBOV) outbreak in West Africa was the largest recorded in history with over 28,000 cases, resulting in >11,000 deaths including >500 healthcare workers. A focused screening and lead optimization effort identified 4b (GS-5734) with anti-EBOV EC50 = 86 nM in macrophages as the clinical candidate. Structure activity relationshi...

Four new quasi-1D Ni2-lantern chain complexes of the form [Ni2(SOCR)4(L)]∞ (R = Ph, L = DABCO (1); R = Ph, L = pyz (2); R = CH3, L = DABCO (3); R = CH3, L = pyz (4)) were prepared from the reaction of [Ni2(SOCR)4(EtOH)], R = CH3 or Ph, with the N,N'-donor bridging ligands pyrazine (pyz) or 1,4-diazabicyclo[2.2.2]octane (DABCO). Reaction of [Ni2(tba...

Cu(I) complexes of the form A[(R3P)Cu(pinF)] were synthesized and characterized, in which (pinF)2- is the bidentate, oxygen-donating, ligand perfluoropinacolate. Low temperature oxygenation of the A[(R3P)Cu(pinF)] species resulted in a trisanionic bis(μ3-oxo) trinuclear Cu(II,II,III) core that was characterized by UV-vis spectroscopy (λmax, nm (ε,...

New ruthenium(II) complexes containing labile nitrile ligands have been prepared by treatment of either the polymer [{RuCl2(COD)}x] (COD = cycloocta-1,5-diene) (1) or its derivative [RuCl2(COD)(NCCH3)2]·NCCH3 (2) with the appropriate nitrile ligands in refluxing acetonitrile under argon. A new route to synthesis of trans-dichlorotetrakis(diphenylph...

Despite the large number of judiciously designed ligands that have been exploited in palladium-catalyzed cross-coupling protocols, the incorporation of ligands bearing appreciable pi-acidic properties has remained significantly underexplored. Herein, we demonstrate that well-defined and low-coordinate Pd-0 complexes supported by m-terphenyl isocyan...

The first X-ray crystal structures of coordination compounds of OP[NC4H8O]3 phosphoric triamide (L) are investigated in Cl2(CH3)2Sn(trans-L)2 (1) and [Mn(H2O)4(trans-L)2]Cl2·2H2O (2) as models of molecular and salt complexes for Hirshfeld surface-based analysis. The crystal packing of 1 includes weak interactions, while in the salt complex 2, a two...

A modular synthesis of tris(aryl)tren ligands has been demonstrated via the condensation of nitrilotracetyl chloride with different anilines followed by reduction. Varying the aniline in the condensation step from 2-methylthioaniline, to 2-phenylthioaniline, to 2-chloroaniline, generates 2,2’,2”-nitrilotris(N-(2-(methylthio)phenyl)acetamide (1), 2,...

We report a variety of experiments and calculations and their interpretations regarding methyl group (CH3) rotation in samples of pure 3-methylglutaric anhydride (1), pure 3-methylglutaric acid (2), and samples where the anhydride is slowly absorbing water from the air and converting to the acid [C6H8O3(1) + H2O → C6H10O4(2)]. The techniques are so...

The recent Ebola Virus (EBOV) outbreak in West Africa was the largest recorded in history with over 28,000 cases, resulting in >11,000 deaths including >500 healthcare workers. A focused screening and lead optimization effort identified 4b (GS-5734) with anti-EBOV EC50=86 nM in macrophages as the clinical candidate. Structure activity relationships...

Presented herein is a general design strategy for the formation of coordinatively unsaturated Mn(I) fragments via the cis labilization of CO using metal carboxylates and subsequent deprotection by a range of abstraction agents. A consistent trend is observed in the ability of carboxylate ligands to facilitate CO dissociation as a function of the el...