Synthesis of cyclopentadienyl ruthenium(II) complexes containing tethered functionalities

The reaction of [C₅H₄(CH₂)_nX]Tl (1: n = 2, X = NMe₂, OMe, CN; n = 3, X = NMe₂) with [(η⁶-C₆H₆)RuCl(μ-Cl)]₂, 2, afforded the sandwich compounds [{η⁵-C₅H₄(CH₂)_nX}Ru(η⁶-C₆H₆)]PF₆, 3, and [η⁵-C₅H₄(CH₂)_nX]₂Ru, 4. Photolytic cleavage of 3 in acetonitrile afforded the tethered products [{η⁵:κN-C₅H₄(CH₂)_nX}Ru(CH₃CN)₂]PF₆, 5.     

2-Pyridylmetallocenes: Part I. Electrophilic halogenation of 2-pyridylferrocene. Molecular structures of 2-pyridylferrocene and its α-brominated and -fluorinated derivatives. Synthesis of 2-pyridylruthenocene and 2-pyridylcymantrene

A new high-yield synthesis of 2-pyridylferrocene (1) without formation of the 1,1′-disubstituted product has been developed. Also the corresponding ruthenocene and cymantrene derivatives [C₅H₄(2-C₅H₄N)]ML_n (ML_n = Ru(C₅H₅) (2), Mn(CO)₃ (3)) were prepared and fully characterized. Ortho-lithiation of 1 followed by electrophilic halogenation yielded [C₅H₃X(2-C₅H₄N)]Fe(C₅H₅) [X = F (4), Cl (5), Br (6), I (7)], with 4 only being the second reported and first fully characterized fluoroferrocene. The molecular structures of 1, 4 and 6 have been determined by X-ray crystallography.     

New arene ruthenium complexes with planar chirality

1,2,4-Trimethyl-cyclohexadiene reacts with RuCl₃ · nH₂O in refluxing ethanol to afford quantitatively [RuCl₂(1,2,4-C₆H₃Me₃)]₂ (1), the coordination of 1,2,4-trimethylbenzene to the ruthenium atom introducing planar chirality at the η⁶-arene ligand. The dinuclear complex 1 reacts with two equivalents of triphenylphosphine (PPh₃) to give quantitatively, as a racemic mixture of enantiomers, [RuCl₂(1,2,4-C₆H₃Me₃)(PPh₃)] (2), the structure of which has been determined by a single-crystal X-ray structure analysis of (rac)-2. Similarly, 1 reacts with two equivalents of the enantiopure phosphine (1S,2S,5R)-(+)-neomenthyldiphenylphosphine (nmdpp) to afford in good yield [RuCl₂(1,2,4-C₆H₃Me₃)(nmdpp)] (3) as a mixture of diastereoisomers, from which the isomer 3a was isolated by crystallisation. A single-crystal X-ray structure analysis of 3a allowed the determination of the absolute configuration at the planar chiral η⁶-arene moiety. Finally, complex 1 reacts with one equivalent of the diphosphine ligand 1,1^′-bis(diphenylphosphino)ferrocene (dppfc) to give the heteronuclear complex [RuCl₂(1,2,4-C₆H₃Me₃) (dppfc)RuCl₂(1,2,4-C₆H₃Me₃)] (4). All complexes were fully characterised by elemental analysis, mass spectrometry, NMR and IR spectroscopies.     

Synthesis and characterization of cyclopentadienyltricarbonyl tungsten selenocarboxylate and selenosulfonate complexes

Cyclopentadienyltricarbonyl tungsten selenocarboxylate complexes CpW(CO)₃SeCOR (1) (R = C₆H₅ (a), 3,5-C₆H₃(NO₂)₂ (b), 3-C₆H₄NO₂ (c), 4-C₆H₄NO₂ (d), CH₃ (e)) and cyclopentadienyltricarbonyl tungsten selenosulfonate complexes CpW(CO)₃SeSO₂R (2) (R = C₆H₅ (a), 4-C₆H₄CH₃ (b), 4-C₆H₄OCH₃ (c), 4-C₆H₄Cl (d), CH₃ (e)) have been prepared from the tungsten anion [CpW(CO)₃Se]⁻ and acid- or sulfonyl chlorides respectively. The new complexes (1 and 2) have been characterized by IR, ¹H NMR spectroscopies as well as elemental analysis. The crystal structure of CpW(CO)₃SeCO-3-C₆H₄NO₂ (1c) was determined.     

Calix[4]arene supported group 5 imido complexes

The reaction of imidoyl chlorides [V(NR)Cl₃] (R = Ph 1, Tol 2, tBu 3) and calix[4]arene methyl ether H₃Mecalix unexpectedly leads to the formation of the structurally characterized vanadium (IV) complex [VCl(Mecalix)] (4). Calix[4]arene methyl ether stabilized imido complexes of the type [V(NR)(Mecalix)] (R = Ph 7, Tol 8, tBu 9) were afforded from the reaction of [V(NR)Cl₃] (R = Ph 1, Tol 2, tBu 3) and the tris(lithium) or tris(sodium) salt of the calix[4]arene ether. The lithium salt [{Li₃(Mecalix)}₂] (5) is a dimer in the solid state, in which two monomeric trianions are bridged by lithium cations. Imido complexes [M(NR)(Mecalix)] (M = Nb: R = tBu, 12, R = Tol 13, R = Mes 14, R = Dipp 15; M = Ta: R = tBu 16, R = Tol 17) (Tol = 4-C₆H₄Me, Mes = 2,6-C₆H₃Me₂; Dipp = 2,6-C₆H₃iPr₂) have been prepared from structurally characterized [NbCl₂(Mecalix)] (10) and previously known [TaCl₂(Mecalix)] (11) via reaction with two equivalents of the appropriately metallated (Li, K) primary amine. The molecular structures of 13 and 15 confirm the mononuclear nature of these complexes.     

Synthesis and characterization of di- and tri-organotin(IV) complexes with Schiff base ligand pyruvic acid 3-hydroxy-2-naphthoyl hydrazone

A series of organotin(IV) complexes with Schiff base ligand pyruvic acid 3-hydroxy-2-naphthoyl hydrazone [R₂SnLY]₂, L = 3-HO-C₁₀H₆-2-CONHNC(CH₃)COOH, R = n-C₄H₉, Y = CH₃OH (1), R = n-C₄H₉, Y = N (2), R = PhCH₂ (3), R = Ph, Y = CH₃OH (4), R = Me, (5) and [R₃SnLY], L = 3-HO-C₁₀H₆-2-CONHNC(CH₃)COOH, R = n-C₄H₉, Y = H₂O, (6), R = Ph (7), R = Me (8) have been synthesized. These complexes have been characterized by elemental analysis, IR, ¹H and ¹¹⁹Sn NMR spectra. The crystal and molecular structure of complexes 1, 2 and 6 have been determined by X-ray single crystal diffraction. Results showed that complex 1 has a dimeric structure and the central tin atom is rendered seven-coordinate in a distorted pentagonal-bipyramid configuration. The complex 2 has a monoclinic structure and the central tin atom is rendered six-coordinate in octahedrally configuration with a planar of SnO₃N unit and two apical aryl C atoms. And the whole structure consists of molecular units connected by weak intermolecular Sn?N and O-H?N interactions. In the complex 6, the central tin atom is five-coordinate in distorted trigonal-bipyramidal geometry.     

New mono and dinuclear arene ruthenium chloro complexes containing ester substituents

The dinuclear arene ruthenium complexes [RuCl₂{C₆H₅(CH₂)₃OCO-p-C₆H₄-OC₈H₁₇}]₂ (1) and [RuCl₂{p-C₆H₄(CH₂COOCH₂CH₃)₂}]₂ (2) have been obtained by dehydrogenation of the corresponding cyclohexadiene derivative with ruthenium chloride hydrate. The single-crystal X-ray structure analysis of 2 shows the arene ligands to be involved in slipped-parallel π-π stacking interactions with neighbouring molecules, thus forming infinite chains along the b-axis. The dinuclear complexes 1 and 2 react with two equivalents of triphenylphosphine (PPh₃) to give in excellent yield the corresponding mononuclear phosphine complexes [RuCl₂{C₆H₅(CH₂)₃OCO-p-C₆H₄-OC₈H₁₇}(PPh₃)] (3) and [RuCl₂{p-C₆H₄(CH₂COOCH₂CH₃)₂}(PPh₃)] (4), respectively. The single-crystal X-ray structure analysis of 4 reveals the formation of a dimer through two C-H?Cl interactions in the solid state.     

C-ansa-zirconocene complexes with O/S donor ligands: Novel homoleptic six coordinate 4-mercaptophenolate complex of Zr(IV)

New C-ansa-zirconocene complexes containing methoxythiophenolate and mercaptophenolate ligands have been synthesized and characterized. The reaction of (HSC₆H₄-n-OMe) (n = 2, 3 or 4) with [Zr{(t-Bu)HC(η⁵-C₅Me₄)(η⁵-C₅H₄)}Me₂] (1) led to the formation of monosubstituted complexes [Zr{(t-Bu)HC(η⁵-C₅Me₄)(η⁵-C₅H₄)}Me(κ,S-SC₆H₄-n-OMe)] (n = 2 (2); n = 3 (3)) and the disubstituted complex [Zr{(t-Bu)HC(η⁵-C₅Me₄)(η⁵-C₅H₄)}(κ,S-SC₆H₄-4-OMe)₂] (4). The complexes [Zr{(R)HC(η⁵-C₅Me₄)(η⁵-C₅H₄)}(κ,O-OC₆H₄-4-SH)₂] (R = t-Bu (6); R = CH₂CHCH₂ (7)) and [Zr(η⁵-C₅H₄)₂(OC₆H₄-n-SH)₂] (n = 3 (9); n = 4 (10)) have been synthesized using the corresponding dimethyl zirconocene and mercaptophenol. However, the reaction of [Zr{(t-Bu)HC(η⁵-C₅Me₄)(η⁵-C₅H₄)}Cl₂] (11) with 4-mercaptophenol in the presence of NEt₃ led to the formation of the first example of a homoleptic six-coordinate mercaptophenolate complex of zirconium, namely [HNEt₃]₂[Zr(κ,O-OC₆H₄-4-SH)₆] (12). Complex 12 can be obtained in higher yield by the reaction of ZrCl₄ with six equivalents of 4-mercaptophenol and NEt_3. The reaction of 12 with [Zr(η⁵-C₅H₄)₂Cl₂] gave the unexpected disubstituted complex [Zr(η⁵-C₅H₄)₂(OC₆H₄-4-SH)₂] (10). The molecular structures of 4 and 12 have been determined by single-crystal X-ray diffraction studies.     

Synthesis and exploratory coordination chemistry of the new ditertiary carbinamine ligand 2,6-bis(α-aminoisopropyl)pyridine

The new pyridine-based N∩N∩N tridentate ligand 2,6-C₅H₃N(CMe₂NH₂)₂ (1) was synthesized by the treatment of 2,6-pyridinedicarbonitrile with an excess of the organocerium reagent in situ generated from CeCl₃ and methyllithium in THF. The reaction of 1 with [RuCl₂(PPh₃)₃] in THF at ambient conditions afforded (OC-6-23)-[RuCl{2,6-C₅H₃N(CMe₂NH₂)₂}(PPh₃)₂]Cl (2). The corresponding dimethyl sulfoxide complex [RuCl{2,6-C₅H₃N(CMe₂NH₂)₂}{S(O)Me₂}₂]Cl (3) was isolated as a mixture of the (OC-6-23) and (OC-6-32) stereoisomers 3a and 3b from the reaction between 1 and (OC-6-22)-[RuCl₂{S(O)Me₂}₃(OSMe₂)] in toluene at 80 °C. A prolonged interaction in toluene at reflux temperature gave isomerically pure 3a. The metal trichloride hydrates MCl₃ · xH₂O (M = Ru, Rh, Ir; x ≅ 2-4) produced mer-[RuCl₃{2,6-C₅H₃N(CMe₂NH₂)₂}] (M = Ru: 4; Rh: 5; Ir: 6), when combined with 1 in refluxing ethanol. The crystal structures of the following compounds were determined: ligand 1 and complexes 2-5 as addition compounds 2 · CH₂Cl₂, 3a · C₇H₈, 4 · EtOH and .     

Synthesis of benzene ruthenium triazolato complexes by [3+2] cycloaddition reactions of activated alkynes and fumaronitrile to benzene ruthenium azido complexes

The dinuclear complex [(η⁶-C₆H₆)Ru(μ-N₃)Cl]₂ (1) is obtained by the reaction of [(η⁶-C₆H₆)RuCl₂]₂ with sodium azide in ethanol. The benzene ruthenium β-diketonato complexes of the general formula [(η⁶-C₆H₆)Ru(L∩L)Cl] {L∩L = O,O′-acac (2); O,O′-bzac (3); O,O′-dbzm (4)} are obtained in methanol by the reaction of [(η⁶-C₆H₆)RuCl₂]₂ with the corresponding β-diketonates. These complexes further react with sodium azide in ethanol to yield complexes of the type [(η⁶-C₆H₆)Ru(L∩L)N₃] [L∩L = O,O′-acac (5); L∩L = O,O′-bzac (6); L∩L = O,O′-dbzm (7)]. The complexes 5-7 are obtained as well by treating 1 with sodium salts of β-diketonates. These neutral benzene ruthenium azido complexes undergo [3+2] dipolar cycloaddition reaction with activated alkynes (MeO₂CCCCO₂Me, EtO₂CCCCO₂Et) or fumaronitrile (NCHCCHCN) to yield the corresponding benzene ruthenium triazolato complexes; [(η⁶-C₆H₆)Ru(O,O′-acac){N₃C₂(CO₂Me)₂}] (8), [(η⁶-C₆H₆)Ru(O,O′-acac){N₃C₂(CO₂Et)₂}] (9), [(η⁶-C₆H₆)Ru(O,O′-acac){N₃C₂HCN}] (10), [(η⁶-C₆H₆)Ru(O,O′-bzac){N₃C₂HCN}] (11) and [(η⁶-C₆H₆)Ru(O,O′-dbzm){N₃C₂HCN}] (12). These complexes are fully characterized on the basis of microanalyses, FT-IR and FT-NMR spectroscopy. The molecular structure of [(η⁶-C₆H₆)Ru(O,O′- acac){N₃C₂(CO₂C₂H₅)₂}] (9) is confirmed by single crystal X-ray diffraction study.     

Nickel promoted C-H, C-C and C-O bond activation in solution

Reaction of NiI₂ with the PCP-ligand {1-Et-2,6-(CH₂PⁱPr₂)₂-C₆H₃} (1) results in selective activation of the strong sp²-sp³ aryl-ethyl bond to afford the aryl-nickel complex [Ni{2,6-(CH₂PⁱPr₂)₂-C₆H₃}I] (2), whereas reaction of NiI₂ with {1,3,5-(CH₃)₃-2,6-(CH₂PⁱPr₂)₂-C₆H} (4) leads to the formation of the benzylic complex [Ni{1-CH₂-2,6-(CH₂PⁱPr₂)₂-3,5-(CH₃)₂-C₆H}I] (5) by selective C-H bond activation. Thermolysis of 5 results in formation of [Ni{2,6-(CH₂PⁱPr₂)₂-3,5-(CH₃)₂-C₆H}I] (6) by activation of the sp²-sp³ C-C bond. The identity of the new 16-electron complexes 2 and 6 was confirmed by reaction of NiI₂ with {1,3-(CH₂PⁱPr₂)₂-C₆H₄} (3) and {1,3-(CH₃)₂-4,6-(CH₂PⁱPr₂)₂-C₆H₂} (7), respectively, lacking the aryl-alkyl groups between the “phosphines arms” (alkyl=ethyl, methyl). Complexes 2 and 5 have been fully characterized by X-ray analysis. Nickel-based activation of an unstrained C-O single bond was observed as well. Reaction of the aryl-methoxy bisphosphine {1-OMe-2,6-(CH₂PⁱPr₂)₂-C₆H₃} (8) with NiI₂ results in the formation of the phenoxy complex [Ni{1-O-2,6-(CH₂PⁱPr₂)₂-C₆H₃}I] (9) by selective sp³-sp³ C-O bond activation.     

Syntheses and characterization of iridium and rhodium ethylene complexes containing a doubly linked cyclopentadienyl ligand

The dimerization of 6,6-dimethylfulvene with Ni(cod)₂ yields the 4,4,8,8-tetramethyl-3a,4,7a,8-tetrahydro-s-indacene isomer (1a). Heating a solution of 1a converts it to the 1,4,5,8 (1b) and 1,4,7,8 (1c) tetrahydro-s-indacene isomers. The activation energy for the isomerization is 23(1) kcal/mol. 1b and 1c can be deprotonated with n-BuLi and the reaction of the dianion with [ClIr(C₂H₄)₂]₂ gives two isomers, cis-[(η⁵-C₅H₃)(CMe₂)Ir(C₂H₄)₂]₂ (cis-2) and trans-[(η⁵-C₅H₃)(CMe₂)Ir(C₂H₄)₂]₂ (trans-2). Reaction of 1b and 1c with RhCl₃ · xH₂O in refluxing methanol yields a red-orange solid, which was consistent with the empirical formula, [(C₅H₃)(CMe₂)RhCl₂]_n (3). Reaction of 3 with C₂H₄ in a Na₂CO₃/ethanol mixture afforded cis-[(η⁵-C₅H₃)(CMe₂)Rh(C₂H₄)₂]₂ in 5% yield.     

Coordination behavior of phosphino-phosphaferrocenes: monodentate versus bidentate coordination to divalent palladium

Two novel phosphino-phosphaferrocenes [η⁵-C₅H₄(CH₂)_nPPh₂]Fe(η⁵-PC₄H₂-2,5-Cy₂) (PP1: n=1; PP2: n=2) have been designed and prepared in order to clarify weak chelate effect in the previously reported (η⁵-C₅H₄CH₂PPh₂)Fe[η⁵-PC₄H₂-2,5-((-)-menthyl)₂] (1). ³¹P NMR studies of reactions of PP1 with PdCl₂(cod) (6) revealed that PP1 showed stronger tendency to coordinate to the Pd^II center in bidentate fashion compared to 1. On the other hand, chelate effect in PP2 was negligibly weak and a reaction of PP2 with 6 in a PP2/6 = 2/1 molar ratio gave a complex PdCl₂(PP2)₂ (10) cleanly in which PP2 coordinated to the palladium center at the PPh₂ moiety as a monodentate ligand. X-ray crystal structure studies of chelate complexes PdCl₂(PP1) (7) and PdCl₂(PP2) (9) showed that 9 had deviations from an idealized geometry in the square planar complex which could be attributed to a larger chelate ring of PP2, while PP1 in 7 constructed nearly ideal geometry for the square planar complex.From comparison of the coordination behavior between 1, PP1, and PP2, it is concluded that steric bulk of (-)-menthyl groups in 1 is the main factor of the weak chelate coordination of 1.     

Investigation on the coordination modes: Syntheses, characterization and crystal structures of diorganotin (IV) dichloride with 4(5)-imidazoledithiocarboxylic acid

A series of diorganotin (IV) complexes of the types of R₂SnCl(SSCC₃H₃N₂) (R = CH₃1, ⁿBu 2, C₆H₅3 and C₆H₅CH₂4), R₂Sn(SSCC₃H₃N₂)₂ (R = CH₃5, ⁿBu 6, C₆H₅7 and C₆H₅CH₂8) and R₂Sn(SSCC₃H₂N₂) (R = CH₃9, ⁿBu 10, C₆H₅11 and C₆H₅CH₂12) have been obtained by reactions of 4(5)-imidazoledithiocarboxylic acid with diorganotin (IV) dichlorides in the presence of sodium ethoxide. All complexes are characterized by elemental, IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectra analyses. Also, the complexes 1, 7 and 9 are characterized by X-ray crystallography diffraction analyses, which reveal that the complex 1 is monomeric structure with five-coordinate tin (IV) atom, the complex 7 is monomeric structure with six-coordinate tin (IV) atom and the complex 9 is one-dimensional chain with five-coordinate tin (IV) atom.     

Transition metal derivatives of 1,10-phenanthroline-5,6-dione: Controlled growth of coordination polynuclear derivatives

The synthesis and the characterization of several mono- and polymetallic derivatives of 1,10-phenanthroline-5,6,-dione (1) are presented.The reaction of 1 with M(CO)₆ (M = Cr, Mo) gives compounds of general formula M(O,O′-C₁₂H₆N₂O₂)₃, M = Cr (2), Mo (3).Compound 3 is also obtained starting from Mo(η⁶-CH₃C₆H₅)₂, whereas the reaction of Cr(η⁶-CH₃C₆H₅)₂ with 1 affords the ionic derivative [Cr(η⁶-CH₃C₆H₅)₂][C₁₂H₆N₂O₂] (4), which has been studied by EPR spectroscopy and DFT calculations.FeCl₂(N,N′-C₁₂H₆N₂O₂)₂ (6), is obtained by thermal decomposition of [Fe(N,N′-C₁₂H₆N₂O₂)₃]Cl₂ (5).Polymetallic compounds of general formula Cr[O,O′-C₁₂H₆N₂O₂-N,N′-MCl₄]₃,containing chromium and a Group 4 element M = Ti (7), Zr (8), Hf (9), are prepared from Cr(O,O′-C₁₂H₆N₂O₂)₃ and the corresponding MCl₄ or MCl₄DME. Polynuclear derivatives of iron and chromium of formula [Fe(N,N′-C₁₂H₆N₂O₂-O,O′-CrCl₂(THF)₂)₃][PF₆]₂ (10), and Cr[O,O′-C₁₂H₆N₂O₂-N,N′-FeCl₂(THF)]₃ (11), are obtained by the reaction of [Fe(N,N′-C₁₂H₆N₂O₂)₃][PF₆]₂ with three equivalents of CrCl₂(THF)₂ and from Cr(O,O′-C₁₂H₆N₂O₂)₃ and FeCl₂(THF)_1.5, respectively. Compound 11 reacts with 1 (3 equivalents in sym-C₂H₂Cl₄ or 6 equivalents in ethanol) to give Cr[O,O′-C₁₂H₆N₂O₂-N,N′-FeCl₂(N,N′-C₁₂H₆N₂O₂)]₃ (12), and [Cr(O,O′-C₁₂H₆N₂O₂-N,N′-Fe(N,N′-C₁₂H₆N₂O₂)₂)₃]Cl₆ (13), respectively.     

Aryldiazenido derivatives: A new entry to the functionalization of Keggin polyoxometalates

A series of aryldiazenido polyoxomolybdates of the type (nBu₄N)₂[Mo₅O₁₃(OMe)₄(NNAr){Na(MeOH)}] (Ar = C₆F₅, 1; Ar = O₂N-o-C₆H₄, 2; Ar = O₂N-m-C₆H₄, 3; Ar = O₂N-p-C₆H₄, 4a; Ar = (O₂N)₂-o,p-C₆H₃, 5) have been obtained by controlled degradation of the parent compounds (nBu₄N)₃[Mo₆O₁₈(NNAr)] with NaOH in methanol. They have been characterized by elemental analysis and UV-Vis and IR spectroscopy. In addition, 4a has been characterized by ⁹⁵Mo NMR spectroscopy and the crystal structure of (nBu₄N)₂[Mo₅O₁₃(OMe)₄(NNC₆H₄-p-NO₂){Na(H₂O))]·H₂O (4b) has been determined by X-ray diffraction. The molecular structure of the anion of 4b features a lacunary Lindqvist-type anion [Mo₅O₁₃(OMe)₄(NNC₆H₄-p-NO₂)]³⁻ interacting with a sodium cation through the four terminal axial oxygen atoms. The 1:1 sodium complexes react with BaCl₂ and BiCl₃ to yield 2:1 complexes which have been isolated as (nBu₄N)₄[Ba{Mo₅O₁₃(OMe)₄(NNAr)}₂] (Ar = C₆F₅, 6; Ar = O₂N-p-C₆H₄, 7) and (nBu₄N)₃[Bi{Mo₅O₁₃(OMe)₄(NNAr)}₂] (Ar = C₆F₅, 8; Ar = O₂N-p-C₆H₄, 9). X-ray crystallography analysis of 9·Me₂CO has shown that the tetradentate [Mo₅O₁₃(OMe)₄(N₂C₆H₄-p-NO₂)]³⁻ anions provide a square-antiprismatic environment for Bi. In contrast, IR spectroscopy provides evidence for a square-prismatic environment of Ba in 6 and 7. In acetonitrile-methanol mixed solvent, [Mo₅O₁₃(OMe)₄(NNAr)]³⁻ and [PW₁₁O₃₉]⁷⁻, generated in situ by alkaline degradation of their respective parents, [Mo₆O₁₈(NNAr)]³⁻ and [PW₁₂O₄₀]³⁻, react together to give the Keggin-type diazenido compounds (nBu₄N)₄[PW₁₁O₃₉(MoNNAr)] (Ar = O₂N-o-C₆H₄, 10; Ar = O₂N-m-C₆H₄, 11; Ar = O₂N-p-C₆H₄, 12), which have been characterized by ³¹P and ¹⁸³W NMR spectroscopy.     

Synthesis, molecular structure, substitution and C-C coupling reactions of ruthenium complexes containing (η-C9H7)Ru(PPh3) as a molecular unit

The 2-methallyl complex [(η⁵-C₉H₇)Ru(η³-2-MeC₃H₄)(PPh₃)] (3), prepared from [(η⁵-C₉H₇)Ru(PPh₃)₂Cl] (2) and 2-MeC₃H₄MgCl, reacts with HX (X = Cl, CF₃CO₂) in the presence of ethene to give the chiral-at-metal compounds [(η⁵-C₉H₇)Ru(C₂H₄)(PPh₃)X] (4, 5) in nearly quantitative yields. Treatment of 2 with AgPF₆ and ethene affords [(η⁵-C₉H₇)Ru(C₂H₄)(PPh₃)₂]PF₆ (6), which reacts with acetone to give the substitution product [(η⁵-C₉H₇)Ru(OCMe₂)(PPh₃)₂]PF₆ (7). The molecular structure of 7 has been determined crystallographically. Whereas treatment of 4 with CH(CO₂Et)N₂ yields the olefin complex [(η⁵-C₉H₇)Ru{η²-(Z)-C₂H₂(CO₂Et)₂}(PPh₃)Cl] (8), the reactions of 4 and 5 with Ph₂CN₂, PhCHN₂ and (Me₃Si)CHN₂ lead to the formation of the carbeneruthenium(II) derivatives [(η⁵-C₉H₇)Ru(CRR′)(PPh₃)Cl] (9-11) and [(η⁵-C₉H₇)Ru(CRR′)(PPh₃)(κ¹-O₂CCF₃)] (12-14), respectively. Treatment of 9 (R = R′ = Ph), 10 (R = H, R′ = Ph) and 11 (R = H, R′ = SiMe₃) with MeLi produces the hydrido(olefin) complexes [(η⁵-C₉H₇)RuH(η²-CH₂CPh₂)(PPh₃)] (15), [(η⁵-C₉H₇)RuH(η²-CH₂CHPh)(PPh₃)] (18a,b) and [(η⁵-C₉H₇)RuH(η²-CH₂CHSiMe₃)(PPh₃)] (19) via C-C coupling and β-hydride shift. The analogous reactions of 11 with PhLi gives the η³-benzyl compound [(η⁵-C₉H₇)Ru{η³-(Me₃Si)CHC₆H₅}(PPh₃)] (20). The η³-allyl complex [(η⁵-C₉H₇)Ru(η³-1-PhC₃H₄)(PPh₃)] (17) was prepared from 10 and CH₂CHMgBr by nucleophilic attack.     

On the identification of ionic species of neutral halogen dimers, monomers and pincer type palladacycles in solution by electrospray mass and tandem mass spectrometry

Electrospray (ESI) mass spectra analysis of acetonitrile solutions of a series of neutral chloro dimers, pincer type, and monomeric palladacycles has enabled the detection of several of their derived ionic species. The monometallic cationic complexes Pd[κ¹-C,κ¹-N,κ¹-S-C(CH₃S-2-C₆H₄)C(Cl)CH₂N(CH₃)₂]⁺ (1a) and [Pd[κ¹-C,κ¹-N,κ¹-S-C(CH₃S-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](CH₃CN)]⁺ (1b) and the bimetallic cationic complex [κ¹-C,κ¹-N,κ¹-S-C(CH₃S-2-C₆H₄)C(Cl)CH₂N(CH₃)₂]Pd-Cl-Pd[κ¹-C,κ¹-N,κ¹-S-C(CH₃S-2-C₆H₄)C(Cl)CH₂N(CH₃)₂]⁺ (1c) were detected from an acetonitrile solution of the pincer palladacycles Pd[κ¹-C,κ¹-N,κ¹-S-C(CH₃S-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](Cl) 1. For the dimeric compounds {Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](μ-Cl)}₂ (2, Y=H and 3, CF₃), highly electronically unsaturated palladacycles [Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂]⁺ (2d, 3d) and their mono and di-acetonitrile adducts, namely, [Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](CH₃CN)]⁺ (2e, 3e) and [Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](CH₃CN)₂]⁺ (2f and 3f) were detected together with the bimetallic complex [Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂]-Cl-Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N](CH₃)₂]⁺ (2a, 3a) and its acetonitrile adducts [κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](CH₃CN)Pd-Cl-Pd[ κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂]⁺ (2b, 3b) and [κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](CH₃CN)Pd-Cl-Pd[κ¹-C, κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂(CH₃CN)]⁺ (2c, 3c). The dimeric palladacycle {Pd[κ¹-C,κ¹-N-C(CH₃O-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](μ-Cl)}₂ (4) is unique as it behaves as a pincer type compound with the OCH₃ substituent acting as an intramolecular coordinating group which prevents acetonitrile full coordination, thus forming the cationic complexes [(C₆H₄(o-CH₃O)CC(Cl)CH₂N(CH₃)₂-κO,κC,κN)Pd]⁺ (4b), [(C₆H₄(o-CH₃O)CC(Cl)CH₂N(CH₃)₂- κO,κC,κN)Pd(CH₃CN)]⁺ (4c) and [(C₆H₄ (o-MeO)CC(Cl)CH₂N(CH₃)₂-κO, κC,κN)Pd-Cl-Pd(C₆H₄(o-CH₃O)CC(Cl)CH₂N(CH₃)₂-κO,κC,κN)]⁺ (4a). ESI-MS spectra analysis of acetonitrile solutions of the monomeric palladacycles Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](Cl)(Py) (5, Y=H and 6, Y=CF₃) allows the detection of some of the same species observed in the spectra of the dimeric palladacycles, i.e., monometallic cationic 2d-3d, 2e-3e and {Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](Py)}⁺ (5a, 6a) and {Pd[κ¹-C,κ¹-N-C(Y-2-C₆H₄)C(Cl)CH₂N(CH₃)₂](CH₃CN)(Py)}⁺ (5b, 6b) and the bimetallic 2a, 3a, 2b, 3b, 2c and 3c. In all cationic complexes detected by ESI-MS, the cyclometallated moiety was intact indicating the high stability of the four or six electron anionic chelate ligands. The anionic (chloride) or neutral (pyridine) ligands are, however, easily replaced by the acetonitrile solvent.     

Phosphane- and phosphite-silver(I) phenolates: Synthesis, characterization and their use as CVD precursors

The silver(I) salts [AgOR] (3a, R = C₉H₆N; 3b, R = C₆H₄-2-CHO, 3c, R = C₆H₄-2-Cl; 3d, R = C₆H₄-2-CN; 3e, R = C₆H₄-2-NO₂) are accessible by the stoichiometric reaction of [AgNO₃] (1) with HOR (2a, R = C₉H₆N; 2b, R = C₆H₄-2-CHO; 2c, R = C₆H₄-2-Cl; 2d, R = C₆H₄-2-CN; 2e, R = C₆H₄-2-NO₂) in presence of NEt₃. Treatment of 3a-3e with PⁿBu₃ (4), P(OMe)₃ (5a) or P(OCH₂CF₃)₃ (5b) in the ratios of 1:1 and 1:2, respectively, produced complexes [L_mAgOR] (L = PⁿBu₃, m = 1: 6a, R = C₉H₆N; 6b, R = C₆H₄-2-CHO; 6c, R = C₆H₄-2-Cl; 6d, R = C₆H₄-2-CN; 6e, R = C₆H₄-2-NO₂. m = 2: 7a, R = C₉H₄; 7b, R = C₆H₄-2-CHO; 7c, R = C₆H₄-2-Cl; 7d, R = C₆H₄-2-CN; 7e, R = C₆H₄-2-NO₂. L = P(OMe)₃, m = 1: 8a, R = C₆H₄-2-CHO; 8b, R = C₆H₄-2-NO₂. m = 2: 9, R = C₆H₄-2-NO₂. L = P(OCH₂CF₃)₃, m = 1: 10, R = C₆H₄-2-NO₂). Based on TGA, temperature-programmed and in situ molecular beam mass spectrometry metal-organic 7e was applied as CVD precursor in the deposition of silver onto glass substrates. The resulting silver films were characterized by XRD. The SEM image of a film grown from 7e at 350 °C showed a homogeneous surface with grain sizes of 40 nm. The molecular structures of 8b and 10 in the solid state were determined. They are isostructural and are cubane-like structured. Low-temperature ³¹P{¹H} NMR studies showed that the title complexes are dynamic in solution and exchange at room temperature their ligands.     

Homobimetallic anthracene-bridged η-cyclopentadienyl derivatives of rhodium(I) and iridium(I): large molecules or supramolecular species?

The reaction of 9,10-bis[(cyclopentadienylmethyl)thallium(I)]anthracene (2), obtained from 9,10-bis(cyclopentadienylmethyl)anthracene (1), with the chloro derivatives of rhodium(I) of formula [RhClL₂]₂ (L=η²-C₈H₁₄ or L₂=η⁴-C₈H₁₂) leads to the corresponding bimetallic complexes [L₂Rh{C₅H₄CH₂(9,10-anthrylene)CH₂C₅H₄}RhL₂] 3 (L=η²-C₈H₁₄) and 4 (L₂=η⁴-C₈H₁₂), in 22.8% and 15.0% yields, respectively. Analogously, by reacting 2 with [IrClL₂]₂ (L=η²-C₈H₁₄ or L₂=η⁴-C₈H₁₂), the corresponding bimetallic iridium(I) complexes [L₂Ir{C₅H₄CH₂(9,10-anthrylene)CH₂C₅H₄}IrL₂] 5 (L=η²-C₈H₁₄) and 6 (L₂=η⁴-C₈H₁₂) were obtained, in 24.5% and 43.0% yields, respectively. All complexes have been characterised by elemental analysis, mass spectrometry, and ¹H NMR. The structure of 4 was elucidated also by single crystal X-ray diffraction: it crystallises in the P2₁/c space group with a=19.932(11), b=6.4417(4), c=12.377(2) Å; α=90°, β=100.90(4)°, γ=90°. V=1560.5(9) ų. Z=2, D_calc=1.606 g cm⁻¹, R₁=0.0449 [I>σ(I)], wR₂=0.1121. The UV-Vis spectra (280-530 nm) of 3-6 are indicative of the existence of strong electronic interactions among the 9,10-anthrylene chromophore and the two cyclopentadienylML₂ moieties. When excited at ca. 370 nm, 1 results to be an efficient light-emitting molecule, while the fluorescence emission of the 9,10-anthrylene chromophore is almost completely quenched in complexes 3-6. The study of the electrochemical behaviour of 3-6 in strictly aprotic conditions allows a satisfactory interpretation of the observed electrode processes and gives information about the location of the redox sites along with the thermodynamic characterisation of the corresponding redox processes. These data show that the occurrence of an intramolecular charge-transfer process between the photo-excited 9,10-anthrylene group and the cyclopentadienylML₂ moiety is a possible route for the observed quenching of emission in the compounds 3-6. The one-electron oxidation of compounds 3-6 by thallium(III) trifluoroacetate leads to the formation of the corresponding cation radicals. Three of them, i.e., 3⁺, 5⁺ and 6⁺, give rise to good X-band EPR spectra that were fully interpreted by computer simulation as well as by semi-empirical calculations (PM3 level) of the spin density distribution.