Silver(I) carbonyl and silver(I) ethylene complexes of a B-protected fluorinated tris(pyrazolyl)borate ligand

B-methylated ligand [MeB(3-(C2F5)Pz)3]-enables the isolation of a lithium adduct [MeB(3-(C2F5)Pz)3]Li with fac-N3F3 coordination, and rare isolable silver carbon monoxide and silver ethylene complexes, [MeB(3-(C2F5)Pz)3]AgCO and [MeB(3-(C2F5)Pz)3]AgC2H4.     

Square-planar iridium(II) and iridium(III) amido complexes stabilized by a PNP pincer ligand

Squaring the circle: the novel dienamido pincer ligand N(CHCHPtBu(2))(2)(-) affords the isolation of the unusual square-planar iridium(II) and iridium(III) amido complexes [IrCl{N(CHCHPtBu(2))(2)}](n) (n=0 (1), +1 (2)). In contrast, the corresponding iridium(I) complex of the redox series (n=-1) is surprisingly unstable. The diamagnetism of 2 is attributed to strong N→Ir π donation.     

Silver(I) and gold(I) complexes of rhodanine

Summary Some rhodanine (HL) complexes of silver(I) and gold(1) have been prepared and studied by conductivity measurements and by i.r. spectroscopy. Structures for the complexes are proposed.     

Silver(I) complexes of thiourea

Ag^I complexes of thiourea (tu) having the general formula Ag(tu) _x NO₃ (x = 1–4) have been prepared and characterized by elemental analyses, i.r. and n.m.r. (¹H, ¹³C, ¹⁵N and ¹⁰⁷Ag) spectroscopy. Separate i.r. bands were observed for terminal and bridging tu ligands in the complexes. The Ag(tu)NO₃ complex is assumed to be polymeric with all tu groups in the bridging mode. A consistent upfield shift in the ¹³C-n.m.r. chemical shift is observed as the number of tu groups attached to Ag^I increases, whereas the opposite trend is observed for ¹H, ¹⁵N and ¹⁰⁷Ag chemical shifts.     

Unsymmetrical (R)PNP(R') pincer ligands and their group 10 complexes

Two new unsymmetrical (R)PNP(R')-type pincer ligands based on a bis(tolyl)amine framework have been synthesized and characterized by a variety of techniques, including X-ray crystallography. These ligands have been coordinated to Ni, Pd, and Pt precursors to provide a number of well-characterized group 10 halides. Conversion of these metal halides to metal hydrides was accomplished using borohydride reagents, or by direct interaction of the ligand with the zerovalent metal precursor. The insertion of oxygen into these hydrides in an attempt to prepare metal hydroperoxides has been examined; however, we were unable to obtain stable and isolable hydroperoxide species.     

Electronic structures of organo-transition-metal complexes I. Silver(I)-Olefin complexes

By using the closed-shell SCF-MO method with the CNDO type approximation for all valence electron systems, the electronic structures of some Ag⁺-olefin complexes are investigated. The calculated values of -H increase with the increasing number of methyl groups on the double bond and this trend agrees with the experimental result. Also calculation reproduces many experimental results, such as the infrared, Raman, and¹³C NMR spectra. These experimental results are discussed on the basis of the calculated electronic structures of Ag⁺-olefin complexes.     

Chlorobis(polyfluorophenyl)thallium(III) complexes and their reactions with gold(I) and tin(II) compounds

The reaction of TlCl₃ with RLi leads to complexes of the general formula TlR₂Cl (R = C₆F₅, p-C₆F₄H, m-C₆F₄H, 2,4,6-C₆F₃H₂, p-C₆FH₄ or m-CF₃C₆H₄). Some of these undergo oxidative addition reactions with gold(I) complexes to give polyfluorophenyl derivatives of the types AuR₂ClL and Au(C₆F₅)R₂(tht) (tht = tetrahydrothiophen), and with SnCl₂ to give oily materials from which stable solids of the general formula Q[SnR₂Cl₃] can be isolated by addition of QCl (Q = Et₄N or Ph₃BzP).     

Iron pyrrole‐based PNP pincer ligand complexes as catalyst precursors

The structure of a pincer ligand consists of a backbone and two `arms' which typically contain a P or N atom. They are tridentate ligands that coordinate to a metal center in a meridional configuration. A series of three iron complexes containing the pyrrole‐based PNP pincer ligand 2,5‐bis[(diisopropylphosphanyl)methyl]pyrrolide (PN^pyrP) has been synthesized. These complexes are possible precursors to new iron catalysts. {2,5‐Bis[(diisopropylphosphanyl)methyl]pyrrolido‐κ³P ,N ,P ′}carbonylchlorido(trimethylphosphane‐κP )iron(II), [Fe(C₁₈H₃₄NP₂)Cl(C₃H₉P)(CO)] or [Fe(PN^pyrP)Cl(PMe₃)(CO)], (I), has a slightly distorted octahedral geometry, with the Cl and CO ligands occupying the apical positions. {2,5‐Bis[(diisopropylphosphanyl)methyl]pyrrolido‐κ³P ,N ,P ′}chlorido(pyridine‐κN )iron(II), [Fe(C₁₈H₃₄NP₂)Cl(C₅H₅N)] or [Fe(PN^pyrP)Cl(py)] (py is pyridine), (II), is a five‐coordinate square‐pyramidal complex, with the pyridine ligand in the apical position. {2,5‐Bis[(diisopropylphosphanyl)methyl]pyrrolido‐κ³P ,N ,P ′}dicarbonylchloridoiron(II), [Fe(C₁₈H₃₄NP₂)Cl(CO)₂] or [Fe(PN^pyrP)Cl(CO)₂], (III), is structurally similar to (I), but with the PMe₃ ligand replaced by a second carbonyl ligand from the reaction of (II) with CO. The two carbonyl ligands are in a cis configuration, and there is positional disorder of the chloride and trans carbonyl ligands.     

Iridium complexes bearing a PNP ligand, favoring facile C(sp3)-H bond cleavage

Hydrogen iodide is lost upon reaction of PNP with IrI(3), where PNP = 2,6-bis-(di-t-butylphosphinomethyl)pyridine to give crystallographically characterized Ir(PNP)*(I)(2), which reacts with H(2) to give Ir(PNP)(H)(I)(2). Ir(PNP)(Cl)(3) is relatively inert towards the intramolecular C-H activation of the tert-butyl's of the PNP ligand.     

Polystyrene anchored rhodium (I) bidentate ligand complexes as catalysts for hydrogenation

Polystyrene supported Rh(I) AA′ (AA′ = anthranilic acid, 2,2′-bipyridine or 1,10-phenanthroline) complexes catalyse the hydrogenation of monoolefins (terminal, cyclic and internal) and dienes. Ethyl sorbate undergoes saturation via the monoene intermediate. Thiscis olefin reacts faster than thetrans isomer. The rate law for the reaction is: Rate α [catalyst] [substrate] [H₂].     

Formation and thermodynamic properties of complexes of Ag(I) with thiourea as ligand

A potentiometric study has been made of the Ag(I)CSN(2)H(4)H(2)O system. Mathematical analysis of the formation functions reveals the existence of the complexes AgCSN(2)H(+)(4), Ag(CSN(2)H(4))(+)(4), Ag(CSN(2)H(4))(+)(3) and Ag(CSN(2)H(4))(+)(4) for which the stability constants have been calculated at different ionic strengths and temperatures. No evidence was found for the formation of polynuclear complexes.     

A thallium mediated route to sigma-arylalkynyl complexes of bipyridyltricarbonylrhenium(I)

A simple, one-pot preparation of rhenium(I) sigma-arylalkynyl complexes is reported using thallium(I) hexafluorophosphate as a halogen abstraction agent. This new route to rhenium sigma-alkynyls enjoys higher yields compared to analogous preparations using silver salts by eliminating potential electrochemical degradation pathways.     

Gold(I) ethylene and copper(I) ethylene complexes supported by a polyhalogenated triazapentadienyl ligand

A rare gold(I) ethylene complex and the closely related copper(I) ethylene adduct have been isolated using [N{(C3F7)C(2,6-Cl2C6H3)N}2]- as the supporting ligand. [N{(C3F7)C(2,6-Cl2C6H3)N}2]Au(C2H4) (1) is an air-stable solid. It features a U-shaped triazapentadienyl ligand backbone and a three-coordinate, trigonal-planar gold center. The copper(I) adduct [N{(C3F7)C(2,6-Cl2C6H3)N}2]Cu(C2H4) (2) also has a similar structure. The 13C NMR signal corresponding to the ethylene carbons of 1 appears at about 64 ppm upfield from the free ethylene, while the ethylene carbons of 2 show a relatively smaller (39 ppm) upfield shift. [N{(C3F7)C(2,6-Cl2C6H3)N}2]M(C2H4) (M=Cu, Au) mediate carbene-transfer reactions from ethyl diazoacetate to saturated and unsaturated hydrocarbons.     

Silver(I) complexes ofN-ethylthiourea. An infrared study

Summary The following silver(I) complexes ofN-ethylthiourea, L, have been isolated in the solid state: AgLX (X = Cl, Br, ClO₄, BF₄, and CF₃CO₂), Ag₂L₃X₂ (X=ClO₄, BF₄ and CF₃CO₂), AgL₂ClO₄, AgL₃X (X = Cl, Br, I, ClO₄, BF₄ and CF₃CO₂). The decrease of the(CS) and (SCN₂) frequencies in the i.r. spectra of the complexes indicates S-coordination of the ligands. The(AgS) frequencies lie in the 267–252 cm^–1 range for terminal and 240-210 cm^–1 range for bridged or long Ag-S bonds. The following structures may be proposed for the complexes. AgLX (X = Cl and Br), polymeric trigonal coordination with bridging halide ions; Ag₂L₃A₂ (A = ClO₄ and BF₄), polymeric trigonal coordination with three bridging sulphur atoms; AgL₂ClO₄, polymeric tetrahedral coordination with four bridging sulphur atoms; AgL₃A (A = ClO₄ and BF₄), dimeric tetrahedral coordination with two terminal and two bridging sulphur atoms; AgLO₂CCF₃ and Ag₂L₃(O₂CCF₃)₂, trigonal and/or tetrahedral coordination with terminal sulphur bonds and bridging CO₂ groups; AgL₃O₂CCF₃, tetrahedral coordination with terminal sulphur bonds and a monodentate CO₂ group. In the trifluoroacetato complexes, a(AgO) band is observed at 185–209 cm^–1. The AgL₃X complexes (X = Cl, Br and I) show two(AgX) and two(AgS) bands with rather low frequencies corresponding to long metal-ligand bond distances.     

Alkaline iodine as an oxidant for thallium (I)

Summary The use of alkaline iodine for the determination of Tl^I has been described. The hypoiodite oxidises Tl^I to Tl^III and the excess oxidant is converted into iodide and iodate which on acidification liberates quantitatively the unreacted iodine. The difference in the initial and back titre value of thiosulphate serves for the direct calculation of the thallium content. The results show a good agreement with the data obtained by a parallel gravimetric and iodometric determination of Tl^III.Sincere thanks of the author are due to Professor S. S. Joshi for kind interest in the work. The award of the Senior Research Fellowship of the National Institute of Sciences of India is also gratefully acknowledged.     

Cu(I) and Ru(II) complexes with elemental phosphorus as ligand: Synthesis and properties

New complexes of Cu(I) and Ru(II) with elemental (white) phosphorus (P₄), [Cu(C₅H-i-Pr₄)(η²-P₄)], [Cu(C₅H-i-Pr₄)(μ,η^2:1-P₄)Cu(C₅H-i-Pr₄)], and [Ru(C₅Me₅)(PCy₃)(η²-P₄)Cl], are synthesized with tetraphosphorus molecule as bidentate η²-ligand. The complexes are obtained by reacting elemental phosphorus with the Cu carbonyl(tetraisopropylcyclopentadienyl) complex [Cu(C₅H-i-Pr₄)(CO)] or with Ru(II) (pentamethylcyclopentadienyl)(tricyclohexylphosphine) chloride, [Ru(C₅Me₅)(PCy₃)Cl]. The structures and compositions of the obtained complexes are studied by ¹H, ³¹P NMR method and elemental analysis. The P₄ molecule is connected to Cu(I) and Ru(II) fragments through the P-P edge due to a side coordination.