Josefa Reyes

Synthesis, reactivity and crystal structure of [Rh(C6H5Me){P(OPh)3}2]ClO4

Abstract The complex [Rh(C 6 H 5 Me){P(OPh) 3 } 2 ]ClO 4 undergoes reactions which give rise to the replacement of the toluence by N- or P-donor ligands, diolefin or arenes and lead to cationic or neutral rhodium(I) complexes. The title compound is monoclinic P 1 /c with a = 14.9559(10), b = 10.1843(5), c = 26.6971(4) A. β = 92.49(1)° and Z = 4. The structure has been determined from three-dimensional data collected by X-rays counter methods. Final R value is 0.034 for 5524 observed independent reflections. The Rh atom appears π-bonded to the arene ring which is puckered, to some extent, as to give a distorted boat-like conformation.

Heterobinuclear pyrazolate-bridged ruthenium(II)rhodium(I), iridium(III)-rhodium(I), and rhodium(III)iridium(I) complexes. Crystal structure of [(p-cymene)Ru(μ-Cl)2(μ-pz)Rh(tetrafluorobenzo[5.6]bicyclo[2.2.2]octan-2,5,7-triene)]

Abstract Heterobinuclear complexes of formula [LMCl 2 (pz)M′(tfb)] (M = Ru, L = p -cymene, M′ = Rh; M = Ir, L = C 5 Me 5 , M′ = Rh; M = Rh, L = C 5 Me 5 , M′ = Ir) and [(C 5 Me 5 )IrCl(pz) 2 Rh(tfb)] (tfb = tetrafluorobenzo[5.6]bicyclo[2.2.2]octan-2,5,7-triene) have been prepared. The molecular structure of [( p -cymene)Ru(μ-Cl)2(μ-pz)Rh(tfb)] has been determined by X-ray diffraction. It consists of two moieties, ( p -cymene)Ru and (tfb)Rh, triply-bridged by a pyrazolate group and two chlorine atoms.

Preparation and x-ray structure of [(C5Me5)Rh(μ-pz)2(μ-CO)Rh(dppp)] BPh4(pz = pyrazolate; dppp = 1,3-bisdiphenylphosphinopropane)

Abstract The cationic complex [(C5Me5)Rh(μ-pz)2(μ-CO)- Rh(dppp)]BPh4 has been prepared by adding 1,3- bisdiphenylphosphinopropane (dppp) and NaBPh4 to a methanol suspension of the neutral compound [(C5Me5)ClRh(μ-pz)2Rh(CO)2]. The structure of the complex was established by X-ray crystallography. It crystallizes in the space group P1 with cell dimensions of a = 15.1870(6), b = 17.5060(8), c = 11.4897(3) A, α = 97.793(3), β = 96.707(2), γ = 94.281(4). The two rhodium atoms are separated by 3.2601(1) A.

Preparation and properties of new triply-bridged DI-μ-pyrazolate (μ-carbonyl) dirhodium complexes with pentamethylcyclopentadienyl and diphosphine ligands

Abstract Cationic complexes of formula [(C 5 Me 5 )Rh(μ-pz) 2 (μ-CO)Rh(L-L)]BPh 4 were prepared by treating a methanolic suspension of [(C 5 Me 5 )ClRh(μ-pz) 2 Rh(CO) 2 ] with NaBPh 4 in the presence of the bidentate ligands L-L (L-L = bis(diphenylphosphino)methane(dppm), 1,4-bis(diphenylphosphino)butane (dppb), cis -1,2-bis(diphenylphosphino)ethylene (dppen), 1,2-bis(diphenylarsino)ethane (dpae)). The intermediate complex [(C 5 Me 5 )Rh(μ-pz) 2 (μ-CO)Rh(CO)(dppen)]BPh 4 was isolated. The formation of the related compounds [(C 5 Me 5 )Rh(μ-pz) 2 (μ-CO)Rh(CO)L]BPh 4 (L = PPh 3 , PCy 3 ) is also reported.

Heterobinuclear IrRh, RuRh and Rulr complexes with pyrazolate bridging ligands: reactivity towards chelating diphosphines; crystal structure of [(C5Me5)Ir(µ-pz)2(µ-CO)-Ir(CO)(dppen)]BPh4·0.5MeOH [pz = pyrazolate, dppen =cis-1,2-bis(diphenylphosphino)ethylene]

Complexes of general formula [LClM(µ-pz)2M′(cod)]1–5[L = C5Me5, M = Rh or Ir; L =p-cymene, Me = Ru; M′= Rh or Ir; pz = pyrazolate; cod = cycloocta-T,5-diene (not all possible combinations)] and [(MeC6H4Pri-p)Ru(µ-pz)(µ-Cl)2Rh(cod)]7 were prepared starting from mononuclear acetylacetonate and pyrazole or pyrazolate-containing moieties. Complexes 1–5 react with CO yielding derivatives [LClM(µ-pz)2M′(CO)2]8–12. Complexes [(C5Me5)ClRh(µ-pz)2Rh(CO)2]13 and [(MeC6H4Pri-p)CIRu(µ-pz)2Ir(CO)2]12 react with NaX to give [(C5Me5)XRh(µ-pz)2Rh(CO)2](X = I, 14; or N3, 15) and [(MeC6H4Pri-p)[graphic omitted]rX(CO)2](X = Br, 16; or I, 17. The dicarbonyl compound 10 and [(MeC6H4Pri-p)CIRu(µ-pz)2M′(CO)2](M′= Rh, 11; or Ir, 12) react with diphosphines (L–L) or 1,2-bis(diphenylarsino)ethane (dpae) and NaBPh4 or AgBF4 affording cationic complexes [LM(µ-pz)2(µ-CO)M′(L–L)]A 23–31[L–L = bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, cis-1,2-bis-(diphenylphosphino)ethylene (dppen) or dpae; A = BPh4 or BF4(not all possible combinations)]. In this reaction intermediates [LM(µ-pz)2(µ-CO)M′(CO)(L–L)]A have been isolated in some cases. The crystal structure of one of these [(C5Me5)Ir(µ-pz)2(µ-CO)Ir(CO)(dppen)] BPh4·0.5MeOH 19 has been determined by X-ray diffraction methods. Crystals are monoclinic, space group P21/c, a= 15.996(2), b= 22.199(4), c= 18.874(3)A, β= 115.04(1)° and Z= 4. The complex cation consists of two iridium atoms bridged by two pyrazolates and one ketonic carbonyl group. An η5-C5Me5 ligand, a chelate dppen and a terminal CO group complete the co-ordination spheres of the iridium atoms, which are separated by 3.440(5)A.

Mixed-valence pyrazolate rhodium complexes. Molecular structure of [(C5Me5)ClRhCl(pz)Rh(tfb)]·CH2Cl2(Hpz = pyrazole; tbf = tetrafluorobenzobarrelene)

Mixed-valence rhodium(III)–rhodium(I) complexes containing pyrazolate(1–)(pz) and/or chlorine groups as bridging ligands have been prepared. The structure of [(C5Me5)ClRhCl(pz)Rh(tfb)]·CH2Cl2[tfb = tetrafluorobenzobarrelene (5,6,7,8-tetrafluoro-1,4-dihydro- 1,4-ethenonaphthalene)], prepared by reacting [Rh(C5Me5)Cl2(Hpz)] with [Rh(acac)(tfb)][acac = acetylacetonate(1–)], has been determined by X-ray diffraction methods. This heterobridged complex is composed of two rhodium atoms (RhIII and RhI) bridged by a chlorine atom and a pyrazolate group. The rhodium–rhodium distance is 3.715(2)A. The preparation and properties of the homobridged neutral and cationic complexes [(C5Me5)XRh(pz)2RhL′2][X = Cl, L2′= tfb, cycle-octa-1,5-diene (cod), (CO)2, or (CO)(NCBut); X = pz, L2′= tfb], [(C5Me5)L″Rh(pz)2RhL2′][ClO4][L″= pyridine (py), McCN, or Hpz, L2′= tfb; L″= py, L′= CO], and [(C5Me5)(Hpz)RhCl2Rh(tfb)][ClO4] are reported.

Homo- and hetero-binuclear complexes containing the anion [Rh(C5Me5){PO(OMe)2}2(pyrazolate)]– as ligand. Crystal structure of [(C5Me5)Rh{µ-PO(OMe)2}2(µ-C3H3N2)-Ru(C6H6)]ClO4·CH2Cl2

The neutral rhodium(III) complex [Rh(C5Me5)I{PO(OMe)2}{P(OH)(OMe)2}] reacts with pyrazole-type ligands [HL = pyrazole (Hpz), 3-methylpyrazole, or 3,5-dimethylpyrazole] in the presence of AgClO4 yielding cationic complexes of the general formula [Rh(C5Me5){PO(OMe)2}{P(OH)(OMe)2}(HL)]ClO4. They react with Na2CO3 in aqueous solutions with formation of the neutral complexes [Rh(C5Me5){PO(OMe)2}2(HL)]. Addition of NaH in tetrahydrofuran to the cationic complexes or thallium acetylacetonate in MeOH to the neutral compounds affords the corresponding bimetallic derivatives [(C5Me5)Rh{PO(OMe)2}2LM](M = Na or Tl). These complexes react with halide compounds such as [{M(ring)Cl2}2][M(ring)= Rh(C5Me5), Ir(C5Me5), Ru(C6H6), Ru(C6H5Me), Ru(MeC6H4Pri-p) or Ru(C6Me6)], [MBr(CO)5], [(PtMe3I)4] or [{Rh(µ–Cl)(cod)}2](cod = cycloocta-1,5-diene) to give cationic or netural complexes of the type [(C5Me5)Rh{µ-PO(OMe)2}2(µ-L)-M(ring)]ClO4 or [(C5Me5)Rh{PO(OMe)2}2(µ-L)MLn][MLn= Re(CO)3, Mn(CO)3, PtMe3 or Rh(cod)]. The crystal structure of [(C5Me5)Rh{µ-PO(OMe)2}2(µ-pz)Ru(C6H6)]ClO4·CH2Cl2 has been determined by X-ray diffraction methods: monoclinic, space group P21/c, a= 11.179(1), b= 17.039(1), c= 18.186(2)A, β= 94.85(1)° and Z= 4. The complex cation consists of one rhodium and one ruthenium atom bridged by two phosphonate and one pyrazolate anion. An η5-C5Me5 and an η6-C6Me6 group complete the co-ordination spheres of the metals, which show no direct intermetallic interaction.

Synthesis and characterization of the alkoxycarbonyl complexes [(C5Me5)M(µ-pz)(µ-I)2Rhl(CO2R)(CO)](M = Rh, R = Me or Et; M = Ir, R = Me; pz = pyrazolate). Molecular structure of [(C5Me5)Ir(µ-pz)(µ-I)2Rhl(CO2Me)(CO)]

The alkoxycarbonyl complexes [(C5Me5)M(µ-pz)(µ-I)2Rhl(CO2R)(CO)][M = Rh, R = Me, (4), or Et, (5); M = Ir, R = Me, (6); pz = pyrazolate] were prepared by treating the corresponding dicarbonyl complex [(C5Me5)ClM(µ-pz)2Rh(CO)2][M = Rh, (1), or Ir, (3)] with molecular iodine in methanol [(4), (6)] or ethanol [(5)] and in the presence of sodium salts (i.e. NaBPh4, NaI·2H2O). The molecular structure of compound (6) was determined by X-ray diffraction: monoclinic space group C2/c with a= 28.574(3), b= 8.688(1), c= 19.321 (2)A, β= 96.44(1)°, and Z= 8. The structure was refined to R= 0.037 for 2 789 observed reflections [F 5.0σ(F)] and 236 parameters. The complex is dinuclear with the two metals, bridged by two iodides and a pyrazolate ligand. The rhodium exhibits distorted-octahedral co-ordination involving three terminal ligands: an iodide, a carbonyl, and a methoxycarbonyl group formed during the preparative reaction.

Five coordinate complexes of the type Rh(SnCl3)(NBD)L2

SummarySeveral new rhodium complexes of general formulation Rh(SnCl3)(NBD)L2 (L=P(OMe)3, P(OMe)2Ph, P(OMe)Ph2, P(OEt)3, P(OEt)2Ph, P(OEt)Ph2, P(O-i-Pr)3, P(OPh)3) have been prepared and characterized by elemental analysis and by i.r. and n.m.r. spectroscopy. The complexes show low or no conductivity in acetone solution and react with carbon monoxide (1 atm).

New thiocarbonyl iridium and rhodium complexes with azolate type ligands

Preparation de complexes de benzimidazolate, imidazolate et de complexes heterodinucleaires tels que [(PPh 3 ) 2 (CS) Rh(μ-RIm) Au(PPh 3 )] ClO 4