Jitendra K. Bera

Chain Compounds Based on Transition Metal Backbones: New Life for an Old Topic

A new link in the chain: After a long period of inactivity, research into one-dimensional compounds based on linear arrays of transition metals is experiencing a renaissance. Recently, oligomeric and polymeric chains have been reported for a variety of transition metals. One such compound of a particularly exotic variety is depicted here, in which a {Pd 4 } 2+ unit is surrounded by a “π-electron sheath” of conjugated polyene ligands.

Bimetallic Catalysis Involving Dipalladium(I) and Diruthenium(I) Complexes

Dipalladium(I) and diruthenium(I) compounds bridged by two [{(5,7-dimethyl-1,8-naphthyridin-2-yl)amino}carbonyl]ferrocene (L) ligands have been synthesized. The X-ray structures of [Pd(2)L(2)][BF(4)](2) (1) and [Ru(2)L(2)(CO)(4)][BF(4)](2) (2) reveal dinuclear structures with short metal-metal distances. In both of these structures, naphthyridine bridges the dimetal unit, and the site trans to the metal-metal bond is occupied by weakly coordinating oxygen from the amido fragment. The catalytic utilities of these bimetallic compounds are evaluated. Compound 1 is an excellent catalyst for phosphine-free, Suzuki cross-coupling reactions of aryl bromides with arylboronic acids and provides high yields in short reaction times. Compound 1 is also found to be catalytically active for aryl chlorides, although the corresponding yields are lower. A bimetallic mechanism is proposed, which involves the oxidative addition of aryl bromide across the Pd-Pd bond and the bimetallic reductive elimination of the product. Compound 1 is also an efficient catalyst for the Heck cross-coupling of aryl bromides with styrenes. The mechanism for aldehyde olefination with ethyl diazoacetate (EDA) and PPh(3), catalyzed by 2, has been fully elucidated. It is demonstrated that 2 catalyzes the formation of phosphorane utilizing EDA and PPh(3), which subsequently reacts with aldehyde to produce a new olefin and phosphine oxide. The efficacy of bimetallic complexes in catalytic organic transformations is illustrated in this work.

Metal–Ligand Cooperation on a Diruthenium Platform: Selective Imine Formation through Acceptorless Dehydrogenative Coupling of Alcohols with Amines

Metal-metal singly-bonded diruthenium complexes, bridged by naphthyridine-functionalized N-heterocyclic carbene (NHC) ligands featuring a hydroxy appendage on the naphthyridine unit, are obtained in a single-pot reaction of [Ru2(CH3COO)2(CO)4] with 1-benzyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (BIN⋅HBr) or 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (PIN⋅HBr), TlBF4, and substituted benzaldehyde containing an electron-withdrawing group. The modified NHC-naphthyridine-hydroxy ligand spans the diruthenium unit in which the NHC carbon and hydroxy oxygen occupy the axial sites. All the synthesized compounds catalyze acceptorless dehydrogenation of alcohols to the corresponding aldehydes in the presence of a catalytic amount of weak base 1,4-diazabicyclo[2.2.2]octane (DABCO). Further, acceptorless dehydrogenative coupling (ADHC) of the alcohol with amines affords the corresponding imine as the sole product. The substrate scope is examined with 1 (BIN, p-nitrobenzaldehyde). A similar complex [Ru2(CO)4(CH3COO)(3-PhBIN)][Br], that is devoid of a hydroxy arm, is significantly less effective for the same reaction. Neutral complex 1 a, obtained by deprotonation of the hydroxy arm in 1, is found to be active for the ADHC of alcohols and amines under base-free conditions. A combination of control experiments, deuterium labeling, kinetic Hammett studies, and DFT calculations support metal-hydroxyl/hydroxide and metal-metal cooperation for alcohol activation and dehydrogenation. The bridging acetate plays a crucial role in allowing β-hydride elimination to occur. The ligand architecture on the diruthenium core causes rapid aldehyde extrusion from the metal coordination sphere, which is responsible for exclusive imine formation.

A Highly Efficient Catalyst for Selective Oxidative Scission of Olefins to Aldehydes: Abnormal-NHC–Ru(II) Complex in Oxidation Chemistry

The utility and selectivity of the catalyst [Ru(COD)(L(1))Br2] (1) bearing a fused π-conjugated imidazo[1,2-a][1,8]naphthyridine-based abnormal N-heterocyclic carbene ligand L(1) is demonstrated toward selective oxidation of C═C bonds to aldehydes and C≡C bonds to α-diketones in an EtOAc/CH3CN/H2O solvent mixture at room temperature using a wide range of substrates, including highly functionalized sugar- and amino acid-derived compounds.

Role of axial donors in the ligand isomerization processes of quadruply bonded dimolybdenum(II) compounds.

Quadruply bonded dimolybdenum(II) complexes with NP-R (2-(2-R)-1,8-naphthyridine; R = thiazolyl (NP-tz), furyl (NP-fu), thienyl (NP-th)) and 2,3-dimethyl-1,8-naphthyridine (NP-Me 2) have been synthesized by reactions of cis-[Mo2(OAc)2(CH3CN)6][BF4]2 with the corresponding ligands. The products cis-[Mo2(NP-tz)2(OAc)2][BF4]2 (1), trans-[Mo2(NP-fu)2(OAc)2][BF4]2 (2), trans-[Mo2(NP-th)2(OAc)2][BF4]2 (3), and trans-[Mo2(NP-Me2)2(OAc)2][BF4]2 (4) were isolated and characterized. The NP-R ligands with stronger R = pyridyl and thiazolyl donors result in cis isomers whereas the weaker furyl and thienyl appendages lead to compounds having a trans orientation of the ligands. The use of NP-Me2 leads to a trans structure with a tetrafluoroborate anion occupying one of the axial sites. Complete replacement of two acetate groups by acetonitrile in 1 and 2 resulted in the cis isomers [Mo2(NP-tz)2(CH3CN)4][OTf]4 (5) and [Mo2(NP-fu)2(CH3CN)4][OTf]4 (6) respectively. The combination of one acetate and two acetonitriles as ancillary ligands, however, yields trans-[Mo2(NP-tz)2(OAc)(CH3CN)2][BF4]3 (7) in the solid state as determined by X-ray crystallography. (1)H NMR spectra of the products are diagnostic of the cis and trans dispositions of the ligands. Solution studies reveal that the ligand arrangements observed in the solid state are mostly retained in the acetonitrile medium. The only exception is 7, for which a mixture of cis and trans isomers are detected on the NMR time scale. The isolation of trans compounds 2- 4 from the cis precursor [Mo2(OAc)2(CH3CN)6][BF4]2 indicates that an isomerization process occurs during the reactions. The mechanism involving acetate migration through axial coordination has been invoked to rationalize the product formation. Compounds 1- 7 were structurally characterized by single-crystal X-ray methods.

Hydrogen-bonding as a tool for building one-dimensional structures based on dimetal building blocks

The ligands isonicotinamide and nicotinamide are used to form assemblies of dimetal (M 2 ) building units via a combination of coordinate bonds and intermolecular hydrogen-bond interactions. Polymeric networks of the linear, zig-zag and sinusoidal varieties are observed in the solid state depending on the ligands and metal precursors involved.

Coupling dirhodium units through terpyridine bridges: synthesis and structure of a novel molecular rectangle

The cation [Rh2(μ-O2CMe)2(MeCN)6]2+ reacts with the bis-terpyridine ligand 2,3,5,6-tetra-2-pyridylpyrazine (tppz) to yield the reduced compound [Rh4(μ-O2CMe)2(tppz)2(MeOH)4]4+ whose structure is that of molecular rectangle with edges defined by short Rh–Rh and long Rh–tppz–Rh units.

Cyclometalated Ir(III) Complexes Containing Pyrazole/Pyrazine Carboxylate Ligands

Two cyclometalated Ir(iii) complexes using 2-phenylpyridine (ppy-H) as the cyclometalating ligand, and pyrazole-3-carboxylic acid (prca-H) and pyrazine 3,5-dicarboxylic acid (pzdca-H2) as ancillary ligands; were synthesized from the chloro-bridged dimer precursor [{(ppy)2Ir}2(μ-Cl)2]. The title compounds [Ir(ppy)2(prca)] (1) and [{Ir(ppy)2}2(pzdca)] (2) are monomeric and dimeric neutral Ir(iii) complexes, respectively. Their electrochemical and photophysical properties were examined. They exhibit metal-based oxidations and ligand-based reductions. These complexes exhibit emission in the blue-green region with lifetimes in the micro-second range at room temperature. The nature of the emission spectra indicates differences in the origin of emission in these two compounds.

Is copper(I) hard or soft? A density functional study of mixed ligand complexes

Fully optimized structures of three- and four-coordinated Ni(0), Cu(I) and Zn(II) complexes with varied combination of hard (H2O or H3N) and soft (H2S, H3P) ligands were computed using density functional theory (DFT). Frequency calculations were carried out to ascertain that the structures were true minima. In the case of Cu(I) and Zn(II), the heat of formation (HOF) values are smaller with larger number of soft ligands. The increase in the HOF on replacing a soft ligand with a hard ligand is less for Cu(I) than for Zn(II). The corresponding HOF is negative for Ni(0) which is not stable with a complement of four hard ligands. The calculated chemical hardness parameters based on vertical ionization potentials clearly indicate the preference of four hard ligands for Zn(II) and four soft ligands for Ni(0). Significantly, the maximum chemical hardness was computed for Cu(I) complex [Cu(PH3)3(NH3)]+, a combination of three soft and one hard ligand. The conclusions derived from absolute hardness data computed for the complexes closely parallel the experimentally observed stability of Cu(I) with an optimum number of hard and soft ligands in its coordination sphere in solution.

Palladium-catalysed direct regiospecific arylation at C5 of thiophenes bearing SO2R substituents at C3

The palladium catalysed direct arylation of thiophenes substituted at C3 by SO2R subtituents was found to be fully selective in favor of carbon C5. This reaction allows the synthesis of a wide variety of 5-aryl-3-sulfonic acid derivatives using as little as 0.5–1 mol% of Pd(OAc)2 as the catalyst in only one step.