Effective Pd-nanoparticle (PdNP)-catalyzed Negishi coupling involving alkylzinc reagents at room temperature

Pd(OAc)(2) is an efficient catalyst precursor for Negishi coupling in the presence of Bu(4)NBr. Secondary and primary alkylzinc reagents with beta-H and arylzinc reagents all reacted with aryl iodides at temperatures as low as -20 degrees C, giving moderate to good yields. One example of coupling between alkynylzinc reagents and aryl iodides was tested and the yield was good. Preliminary kinetic studies indicated that the process involved PdNPs as the active catalytic species.     

The chemistry of orqanobismuth reagents: Part XIII ligand coupling induced by Pd(O)

Palladium zero converts triphenylbismuth quantitatively to diphenyl and metallic bismuth. Many other derivatives of Bi (III) and Bi(V) are similarly transformed to diaryls in excellent yield. Similar reactions with triphenylantimony and with perphenyl lead derivatives suggest that a number of non-transition metal elements should show similar behaviour.Acid chlorides also react under mild conditions with triphenylbismuth under catalysis by palladium (O) to furnish phenylketones in excellent yield (with respect to the triphenylbismuth). All three phenyls are transferred when a suitable excess of the acid chloride is used. Diaryl formation is a minor side reaction.     

Formation and reactions of alkylzinc reagents in room-temperature ionic liquids

[reaction: see text] The presence of a suitable amount of bromide or chloride ions was found to be critical in forming the alkylzinc reagents from alkyl iodides and zinc metal in the room-temperature ionic liquid, N-butylpyridinium tetrafluoroborate. Beta-hydride transfer in the reactions of butylzinc reagents with aldehydes can also be reduced by a bromide ion.     

First stereospecific synthesis of (E)- or (Z)-alpha-fluoroenones via a kinetically controlled Negishi coupling reaction

A highly stereospecific synthesis of (E)- or (Z)-alpha-fluoro-alpha,beta-unsaturated ketones 4, via a kinetically controlled Negishi palladium-catalyzed coupling reaction, was developed, providing an easy and general access to valuable fluorinated intermediates (pharmaceutical, peptide mimic, and so on). The synthesis involved a reaction between E/Z gem-bromofluoroolefins 2 and alkoxyvinylzinc species 6 under controlled reaction temperature. At 10 degrees C, (Z)-4 (70 to 99% yields) was obtained along with unreacted (Z)-2 (66 to 99% yields). At THF reflux, the recovered olefin was transformed into (E)-4 (up to 98% yield).     

Negishi coupling strategy of a repetitive two-step method for oligoarene synthesis

A novel repetitive two-step method for oligoarene synthesis, based on Negishi cross-coupling of zinciophenoxides or zinciopyridinoxides with aryl triflates and subsequent triflation of the hydroxy group, was developed. Reaction conditions were optimized for the preparation of the arylzinc compounds and the palladium-catalyzed cross-coupling step.     

Five coordinate rhodium(I) olefin complexes containing the ligand bis(but-3-enyl)phenylphosphine

The complexes Rh₂X₂(bbp)₂ (X = Cl, Br or I; and bbp = bis(but-3-enyl)phenylphosphine) have been prepared. These complexes have been characterized as five coordinate dimers in which the unsaturated phosphine acts as a tridentate ligand. Carbon monoxide reacts reversibly with the dimers forming the five coordinate monomeric compounds RhX(CO)(bbp). Mass spectral, infrared, Raman, and proton magnetic resonance data are consistent with the above formulations.     

Magnetic properties of a manganese(II) trinuclear complex involving a tridentate Schiff-Base ligand

The Schiff condensation of 2-pyridinecarboxaldehyde N-oxide with 2-aminophenol gave a tridentate ligand, abbreviated as Hpoxap. This ligand bears the functionality of a terminating group in a trinuclear complex [Mn(poxap)Mn(ac)4Mn(poxap)], where ac- is the acetate bridge. The magnetic data were treated simultaneously during the fitting procedure with the spin Hamiltonian containing isotropic exchange, the zero-field splitting parameters, and the molecular-field correction and resulted in JMn-Mn/hc = -4.73 cm-1, gMn(t) = 1.96, DMn(t)/hc = -0.45 cm-1, and zj/hc = +0.45 cm-1 with ground state S = 5/2, where t = terminal atom. At low temperature, the features of a ferromagnetic correlation become evident.     

Complexes of platinum(II) and palladium(II) involving thiohydantoin as a bidentate ligand

Summary K₂PtCl₄ and K₂PdCl₄ react with thiohydantoin (2 moles) to give new types of bidentate chelate complexes PtL₂ · 2H₂O and PdL₂ · 2H₂O, where L is the deprotonated ligand. With palladium the rate of reaction is very fast, whereas in the platinum case reaction occurs stepwise allowing isolation and characterization, by elemental analysis, n.m.r. and by i.r. spectroscopy, of intermediate species.     

Copper(ii) complexes of a polydentate imidazole-based ligand. pH effect on magnetic coupling and catecholase activity

A potentially dodecadentate N8O4-donor ligand obtained from 2,2'-biimidazole and l-valine and its tetranuclear Cu(ii) complexes in different degrees of protonation were characterized by chemical and spectroscopic methods. The extensive solution studies performed reveal that the rise in pH media leads successively to the formation of imidazolato (pKa(1) and pKa(2) and hydroxido (pKa(3) and pKa(4)) bridges. A frozen solution EPR study shows a decrease in the signal intensity until an EPR silent spectrum is observed, upon increasing the basicity of the solution. The catalytic performance of the oxidation of 3,5-di-tert-butylcatechol to its corresponding quinone was studied using UV-Vis-NIR absorption spectroscopic methods in CH3CN-H2O and in CH3OH-H2O at pH = 7.5, 8.0 and 8.5. A marked increase in activity, consistent with the formation of the hydroxide bridged species, is observed at pH = 8.5 in both solvent mixtures, but the activity is significantly higher in CH3OH-H2O.     

Insights into the elementary steps in Negishi coupling through kinetic investigations

The Negishi coupling has been widely applied in organic synthesis, while relevant mechanistic studies are relatively rare. To obtain an understanding of the fundamental steps in the Negishi coupling, oxidative addition, transmetalation and reductive elimination, the kinetic investigation has served as one of the most important strategies. In this review, insights into the elementary steps in the Negishi coupling through kinetic investigations are summarized.     

Iron(I) in Negishi cross-coupling reactions

Herein we demonstrate both the importance of Fe(I) in Negishi cross-coupling reactions with arylzinc reagents and the isolation of catalytically competent Fe(I) intermediates. These complexes, [FeX(dpbz)(2)] [X = 4-tolyl (7), Cl (8a), Br (8b); dpbz = 1,2-bis(diphenylphosphino)benzene], were characterized by crystallography and tested for activity in representative reactions. The complexes are low-spin with no significant spin density on the ligands. While complex 8b shows performance consistent with an on-cycle intermediate, it seems that 7 is an off-cycle species.     

Influence of terpyridine as pi-acceptor ligand on the kinetics and mechanism of the reaction of NO with ruthenium(III) complexes

The kinetics of the unusually fast reaction of cis- and trans-[Ru(terpy)(NH3)2Cl]2+ (with respect to NH3; terpy=2,2':6',2"-terpyridine) with NO was studied in acidic aqueous solution. The multistep reaction pathway observed for both isomers includes a rapid and reversible formation of an intermediate Ru(III)-NO complex in the first reaction step, for which the rate and activation parameters are in good agreement with an associative substitution behavior of the Ru(III) center (cis isomer, k1=618 +/- 2 M(-1) s(-1), DeltaH(++) = 38 +/- 3 kJ mol(-1), DeltaS(++) = -63 +/- 8 J K(-1) mol(-1), DeltaV(++) = -17.5 +/- 0.8 cm3 mol(-1); k -1 = 0.097 +/- 0.001 s(-1), DeltaH(++) = 27 +/- 8 kJ mol(-1), DeltaS(++) = -173 +/- 28 J K(-1) mol(-1), DeltaV(++) = -17.6 +/- 0.5 cm3 mol(-1); trans isomer, k1 = 1637 +/- 11 M(-1) s(-1), DeltaH(++) = 34 +/- 3 kJ mol(-1), DeltaS(++) = -69 +/-11 J K(-1) mol(-1), DeltaV(++) = -20 +/- 2 cm3 mol(-1); k(-1)=0.47 +/- 0.08 s(-1), DeltaH(++)=39 +/- 5 kJ mol(-1), DeltaS(++) = -121 +/-18 J K(-1) mol(-1), DeltaV(++) = -18.5 +/- 0.4 cm3 mol(-1) at 25 degrees C). The subsequent electron transfer step to form Ru(II)-NO+ occurs spontaneously for the trans isomer, followed by a slow nitrosyl to nitrite conversion, whereas for the cis isomer the reduction of the Ru(III) center is induced by the coordination of an additional NO molecule (cis isomer, k2=51.3 +/- 0.3 M(-1) s(-1), DeltaH(++) = 46 +/- 2 kJ mol(-1), DeltaS(++) = -69 +/- 5 J K(-1) mol(-1), DeltaV(++) = -22.6 +/- 0.2 cm3 mol(-1) at 45 degrees C). The final reaction step involves a slow aquation process for both isomers, which is interpreted in terms of a dissociative substitution mechanism (cis isomer, DeltaV(++) = +23.5 +/- 1.2 cm3 mol(-1); trans isomer, DeltaV(++) = +20.9 +/- 0.4 cm3 mol(-1) at 55 degrees C) that produces two different reaction products, viz. [Ru(terpy)(NH3)(H2O)NO]3+ (product of the cis isomer) and trans-[Ru(terpy)(NH3)2(H2O)]2+. The pi-acceptor properties of the tridentate N-donor chelate (terpy) predominantly control the overall reaction pattern.     

Binding of pi-acceptor ligands to (triamine)iron(II) complexes

A series of (Me3TACN)FeII derivatives with soft coligands have been investigated, where Me3TACN is N,N',N"-trimethyl-1,4,7-triazacyclononane. Treatment of Me3TACN with FeCl2 afforded a compound with the empirical formula (Me3TACN)FeCl2 (1). Compound 1, which is a versatile precursor reagent, was shown by single-crystal X-ray diffraction to be the salt [(Me3TACN)2Fe2Cl3][(Me3TACN)FeCl3], containing isolated [(Me3TACN)2Fe2Cl3]+ and [(Me3TACN)FeCl3]- subunits. Treatment of 1 with NaBPh4 gave the known [(Me3TACN)2Fe2Cl3]BPh4, while the addition of Me3TACN to FeCl4(2-) gave [(Me3TACN)FeCl3]-. Oxygenation of 1 afforded [(Me3TACN)FeCl2]2(mu-O), which was shown crystallographically to be centrosymmetric with a pair of distorted octahedral Fe centers. The Fe-N bond trans to the Fe-O bond is elongated by 02 A relative to the other Fe-N distances. Solutions of 1 and thiolates absorb CO to give [(Me3TACN)Fe(SPh)(CO)2]BPh4 and (Me3TACN)Fe(S2C2H4)(CO) (nu CO = 1896 cm-1). Treatment of 1 with excess CN- afforded [(Me3TACN)Fe(CN)3]-, isolated as its PPh4+ salt 5. Crystallographic and spectroscopic studies show that 5 is low spin with a C3v structure; its Fe-N distances contracted by 023 A relative to those in [(Me3TACN)FeCl3]-. Aqueous solutions of 1 bind CO upon the addition of CN- to produce (Me3TACN)Fe(CN)2(CO) (6) Analogous to 6 is (Me3TACN)Fe(CN)2(CNMe), prepared by methylation of 5. The metastable dicarbonyl [(Me3TACN)FeI(CO)2]I was prepared by treatment of FeI2(CO)4 with Me3TACN and was crystallographically characterized as its BPh4- salt. Values of E1/2 for [(Me3TACN)FeCl3]-, 5, and 6 are -0409, -0640, and 0533 V vs Fc/Fc+, respectively.     

Controlling regiochemistry in Negishi carboaluminations. Fine tuning the ligand on zirconium

The species on the zirconocene catalyst is changed from two Cp's to the Brintzinger ligand and catalytic amounts of MAO are used to usually effect a >99% regiocontrol of Negishi carboaluminations of 1-alkynes in toluene.     

Consideration of spin-orbital coupling in olefin ozonolysis

Possible S-T crossings along the olefin ozonolysis pathway were examined. Spin-orbital coupling inducing S-T transitions in the Criegee intermediate near the activation barrier were explained. The role of states with different symmetry and orbital characteristics (σσ and σπ) participating in S-T transitions during a chemical transformation was noted. Cherkassy Engineering and Technology Institute, 460 Shevchenko Boulevard, 257006 Cherkassy, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 2, pp. 67–71, March–April, 1997.     

Synthesis of (hetero)arylated pyridazin-3(2H)-ones via Negishi reaction involving zincated pyridazin-3(2H)-ones

Zincated pyridazin-3(2H)-ones generated via bromine-magnesium exchange followed by transmetalation using ZnCl(2) or via lactam-directed ortho C4-H zincation with TMPZnCl·LiCl have been synthesized. These in situ created organometallics can be used in Negishi reactions with iodo(hetero)arenes delivering a new approach toward (hetero)arylpyridazin-3(2H)-ones.     

Synthesis of (1-adamantylimido)vanadium(V) complexes containing aryloxo, ketimide ligands: effect of ligand substituents in olefin insertion/metathesis polymerization

A series of (1-adamantylimido)vanadium(V) complexes containing anionic donor ligands of the type, V(NAd)Cl2(L) [Ad = 1-adamantyl; L = O-2,6-Me2C6H3 (2), O-2,6-(i)Pr2C6H3 (3), NC(t)Bu2 (5), NC((t)Bu)CH2SiMe3 (6), NC((t)Bu)Ph (7), NCPh2 (8)], have been prepared from V(NAd)Cl 3, which was in turn prepared from VOCl3 by treatment with 1-adamantylisocyanate in octane, by treatment with the corresponding lithium salts (lithium phenoxides, lithium ketimides) in Et2O. These complexes (2, 3, 5-8) were identified by NMR spectroscopy and elemental analysis, and the structures for 2 and 5 were determined by X-ray crystallography. The reaction of V(NAd)Cl3 with 2,6-dimethylphenol in n-hexane afforded the tris(aryloxo) analogue V(NAd)(O-2,6-Me2C6H3)3 (4), the structure of which was determined by X-ray crystallography. 8 gradually decomposed in toluene to give a dimeric species, [N(Ad)H3](+)[V2(mu2-Cl)3Cl2(NAd)2(NCPh2)2](-) (10), but 8 was stabilized as a PMe 3 coordinated species, V(NAd)Cl2(NCPh2)(PMe3)2 (9): the structures for 9 and 10 were determined by X-ray crystallography. These complexes were evaluated as catalyst precursors for ethylene polymerization in the presence of MAO. The ketimide analogues, especially 5, exhibited moderate catalytic activity, and the activity with a series of V(NAd)Cl2(L)-MAO catalyst systems increased in the order: L = NC(t)Bu2 (5, 516 kg-PE/mol x V x h) > NC((t)Bu)Ph (7, 300) > NCPh2 (8, 105) > NC((t)Bu)CH2SiMe3 (6, 70.8). These complexes (2, 3, 5, 6) were found to be effective as catalyst precursors for the ring-opening metathesis polymerization (ROMP) of norbornene (NBE) in the presence of MeMgBr and PMe3.