Presence Of NH4PF6 Research Articles

Synthese und Reaktionen der Metall‐Base [(C5Me4H)Co(PMe3)2

Synthesis and Reactions of the Metal Base [(C5Me4H)Co(PMe3)2]The (tetramethylcyclopentadienyl)cobalt complex [(C5Me4H)Co(PMe3)2] (1), which is prepared from [CoCl(PMe3)3] and LiC5Me4H in 75% yield, behaves like a Lewis base and reacts with NH4PF6, CH3I, or CF3SO3CH3 by oxidative addition to give the cations [(C5Me4H)CoX(PMe3)2]+ (X = H, I, CH3; 2–4) isolated as PF6 salts. From 3 (X = I) and excess LiCH3 the dimethylcobalt(III) compound [(C5Me4H)Co(CH3)2(PMe3)] (5) is obtained. Treatment of the corresponding trifluoroacetato derivative [(C5Me4H)Co(PMe3)(OCOCF3)2] (6) with PMe3, P(OMe)3, and 1,2‐C6H4(PPh2)2 leads, in the presence of NH4PF6, to the formation of the cationic complexes 7–9. The displacement of the two PMe3 ligands in 1 by (Ph2P)2NMe gives the rather unstable chelate compound {(C5Me4H)Co[(Ph2P)2NMe]} (10), which on treatment with NH4PF6 is transformed into the stable complex {(C5Me4H)CoH[(Ph2P)2NMe]}PF6 (11). The structure of 11 has been determined by X‐ray diffraction methods.

Osmium thioether chemistry: synthesis and single-crystal X-ray structures of [Os([9]aneS3)2][PF6]2·2MeNO2, [Os(4-MeC6H4Pri)([9]aneS3)][BPh4]2·MeNO2and [OsH(CO)(PPh3)([9]aneS3)]PF6·0.5CH2Cl2([9]aneS3= 1,4,7-trithiacyclononane)

Treatment of [{OsCl2(4-MeC6H4Pri)}2] with 4 molar equivalents of [9]aneS3 in EtOH for 48 h followed by addition of NH4PF6 affords the bis(sandwich) complex [Os([9]aneS3)2][PF6]2 in 55% yield. An alternative and more direct route is by reaction of [NH4]2[OsCl6] with 2 molar equivalents of [9]aneS3 in refluxing water–dimethylformamide–MeOH (3 : 1 : 1 v/v/v) for 48 h followed by addition of NH4PF6. The complex [Os([9]aneS3)2][PF6]2·2MeNO2 crystallises in the monoclinic space group P21/a(alt. P21/c, no. 14) with a= 9.6621(5), b= 15.1573(8), c= 10.6367(7)A, β= 100.524(5)° and Z= 2. A single-crystal X-ray structure determination shows a centrosymmetric cation with homoleptic thioether co-ordination at OsII, Os–S(1) 2.3313(18), Os–S(4) 2.3380(19) and Os–S(7) 2.3408(20)A, consistent with a d6 metal centre. The ion [Os([9]aneS3)2]2+ shows a reversible oxidation at E½=+1.16 V vs. ferrocene–ferrocenium. Coulometry confirms this oxidation to be a one-electron process. Electrochemical or chemical oxidation of [Os([9]aneS3)2]2+ gives [Os([9]aneS3)2]3+ which has been characterised by electronic and ESR spectroscopy. Reaction of [{OsCl2(4-MeC6H4Pri)}2] with 2 molar equivalents of [9]aneS3 in MeOH followed by addition of NaBPh4 affords the mixed-sandwich complex [Os(4-MeC6H4Pri)([9]aneS3)][BPh4]2 in 65% yield. The complex [Os(4-MeC6H4Pri)([9]aneS3)][BPh4]2·MeNO2 crystallises in the triclinic space group P, a= 11.5027(8), b= 13.8509(13), c= 18.3983(12)A, α= 94.72(1), β= 105.01(3)γ= 91.28(1)° and Z= 2. The crystal structure shows facial co-ordination of both [9]aneS3 and 4-MeC6H4Pri at octahedral OsII. Interestingly, there is an unusual disorder of the trithia macrocycle with two enantiomers of [9]aneS3 being present in the crystal: the two forms of the macrocycle were successfully modelled. Reaction of [MH2(CO)(PPh3)3] with 1 molar equivalent of [9]aneS3 in the presence of NH4PF6 in refluxing acetone (M = Ru) or refluxing 2-methoxyethanol (M = Os) for 2 h under N2 gives [MH(CO)(PPh3)([9]aneS3)]PF6. The complex [OsH(CO)(PPh3)([9]aneS3)]PF6·0.5CH2Cl2 crystallises in the monoclinic space group P21/n(alt. P21/c, no. 14) with a= 15.955(6), b= 21.929(9), c= 8.895(7)A, β= 96.69(8)° and Z= 4. The structure shows octahedral OsII with [9]aneS3 bound facially, Os–S(1) 2.377(3)(trans to CO), Os–S(4) 2.369(3)(trans to PPh3), Os–S(7) 2.402(3)(trans to H), Os–H 1.60(9), Os–P 2.3344(24) and Os–C 1.868(11)A. The reactivity of [MH(CO)(PPh3)([9]aneS3)]+ with O2 and chlorinated solvents is discussed.

ChemInform Abstract: Rational Synthesis of Metalla‐Sulfur‐Nitrogen Complexes: Use of (Me2SnS2N2)2 in the Preparation of Complexes of the Type (M(S2N2H)(PR3)2)X (M: Pt or Pd). X‐Ray Structures of (Pt(S2N2H)(PEt3)2) (Me2SnCl3), (Pt(S2N2H)(PnBu3)2)2(PF6)Cl, and ((Co(S2N2H)2)2(Ph2P(O)CH2CH2P(O)Ph2)).

AbstractReaction of (Me2SnS2N2)2 (II) with cis‐complexes (I) yields the title complexes (IIIa), (IIIb) or, in the presence of NH4PF6, the PF6‐ salts (IIIc), (IIId) or (IV).

Areneruthenium(II) carboxylates: reactions with ligands and the X-ray structure of the p-cymene pyrazine complex [Ru(η-p-MeC6H4CHMe2)Cl(pyz)2]PF6

The preparation of monomeric areneruthenium(II) acetates and trifluoroacetates [Ru(η-arene)X(O2CR)] and [Ru(η-arene)(O2CR)2](X = Cl or Br; R = Me or CF3; arene = C6H6, p-MeC6H4CHMe2, C6H3Me3-1,3,5, C6H2Me4-1,2,4,5, or C6Me6)(not all possible combinations) from the corresponding dihalides [{Ru(η-arene)X2}2] is described. Infrared spectra suggest that the complexes [Ru(η-arene)X(O2CR)] contain a bidentate carboxylate group and that [Ru(η-arene)(O2CR)2] contain one bi- and one uni-dentate carboxylate group, which are apparently equivalent on the n.m.r. time-scale at room temperature. Reaction of trifluoroacetic acid with [{Ru(η-C6Me6)Cl2}2] gives a complex of empirical formula Ru(η-C6Me6)Cl(O2CCF3)·CF3CO2H which may be a salt [(η-C6Me6)Ru(η-Cl)2(µ-O2CCF3)Ru(η-C6Me6)][H(O2CCF3)2]·CF3CO2H. Triphenylphosphine converts [Ru(η-C6Me6)(O2CR)2](R = Me or CF3) into [Ru(η-C6Me6)(O2CR)2(PPh3)] in which both carboxylate groups are unidentate. The trifluoroacetate group is completely displaced from [Ru(η-C6H6)Cl(O2CCF3)] by pyridine (py) or ethyldiphenylphosphine to give [Ru(η-C6H6)ClL2]+(L = py or PEtPh2), isolated as PF6– or BPh4– salts. The potentially binucleating ligands pyrazine (pyz), 4,4′-bipyridyl, and 1,3-dithiane react either with [Ru(η-C6H6)Cl(O2CCF3)] or with [{M(η-p-MeC6H4CHMe2)Cl2}2](M = Ru or Os) in the presence of NH4PF6 or NaBPh4 in methanol to give [M(η-arene)ClL2]+ salts in which only one donor atom of the ligand is co-ordinated, but pyz and [{Ru(η-p-MeC6H4CHMe2)Cl2}2] react in dry tetrahydrofurane to give the pyrazine-bridged species {Ru(η-p-MeC6H4CHMe2)Cl2}2(µ-pyz). The structure of the complex [Ru(η-p-MeC6H4CHMe2)Cl(pyz)2]PF6 has been verified by X-ray analysis. The crystals are triclinic, space group P, with a= 9.265(2), b= 9.684(4), c= 12.969(2)Å, α= 86.51(2), β= 72.89(2), and γ= 85.59(2)°.

Cyclopentadienyl-ruthenium and -osmium chemistry. XIX. Some complexes containing η2-olefin, η2-allene and η2-alkyne ligands

Reactions between RuCl(Pme3)2(η-C5H5) and unsaturated hydrocarbons in the presence of NH4PF6 have given [Ru(η2-un)(PMe3)2(η-C5H5)] PF6[un = C2H4, (E)-CH(CN)=CH(CN),CH2=CHCH=CH2, CH2=C=CH2, CH2=C=CMe2, C2Ph2, PhC2C2Ph, PhC2CO2Et, C2(CO2Me)2 and C2(CF3)2]. The molecular structures of the buta-1,3-diene (3) and allene (4) complexes have been determined. In both compounds, the unsaturated hydrocarbon is bonded to ruthenium in an asymmetric η2 mode: Ru-C 2.185, 2.242(5) [for (3)], 2.084, 2.172(6) [for (4)l; coordinated C=C 1.386(8), 1.394(8) A, respectively. The allene skeleton is bent by 35� at the central carbon. Crystal data: (3) monoclinic, P21/n, a 17.343(2), b 13.692(4), c 17.997(3) �, β 94.91(1)�, Z 8; (4) orthorhombic, Pca21, a 18.999(3), b 9.253(3), c 23.016(6) �, Z 8. The structures were refined to residuals of R 0.026, R, 0.028 for 4076 data with 1 > 2.5σ(I) [for (3)], and R 0.022, Rw 0.024 for 3054 data [for (4)].

Cyclopentadienyl-ruthenium and -osmium chemistry. XIII. Some complexes containing isonitrile ligands

Reactions between isonitriles and RuCl(PPh3)2(η-C5H5) have given RuCl(CNR)(PPh3)(η-C5H5)(R = But, c-C6H11, CH2S02C6H4Me-p or C6H40Me-p) and RUCl(CNBut)2(η-C5H5); in the presence of NH4PF6, cationic complexes [RU(CNR)(PPh3)2(η-C5H5)]PF6 (R = But, c-C6H11 or CH2SO2C6H4Me-p) and [RU(CNBut)2(PP~h3)(η-C5H5)]PF6 were obtained. Protonation of Ru(CN)- (PPh3)2(η-C5H5) gives the hydrogen isocyanide derivative [Ru(CNH)(PPh3)2(η-C5H5)]PF6; tri- alkyloxonium salts alkylate the cyano complex affording [Ru(CNR)(PPh3)2(η-C5H5)]PF6 (R = Me or Et).