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1.
Reaction of (C5H5)2Ti(CH3)2 or (CH3)4C2(C5H4)2Ti(CH3)2 with pyridine-2,6-dicarboxylic acid (dipicolinic acid) yields titanocene dipicolinate derivatives. The molecular structure of (C5H5)2Ti dipicolinate is that of an axially symmetric, pentacoordinate titanocene derivative with two carboxyl oxygen atoms and the pyridine nitrogen atom as ligating atoms. Two identical chelate bite angles of only 71° make the dipicolinate ligand particularly suited to form a remarkably stable titanocene derivative with unprecedented pentacoordintae geometry.  相似文献   

2.
A facile and general synthetic pathway for the production of dearomatized, allylated, and C? H bond activated pyridine derivatives is presented. Reaction of the corresponding derivative with the previously reported reagent bis(allyl)calcium, [Ca(C3H5)2] ( 1 ), cleanly affords the product in high yield. The range of N‐heterocyclic compounds studied comprised 2‐picoline ( 2 ), 4‐picoline ( 3 ), 2,6‐lutidine ( 4 ), 4‐tert‐butylpyridine ( 5 ), 2,2′‐bipyridine ( 6 ), acridine ( 7 ), quinoline ( 8 ), and isoquinoline ( 9 ). Depending on the substitution pattern of the pyridine derivative, either carbometalation or C? H bond activation products are obtained. In the absence of methyl groups ortho or para to the nitrogen atom, carbometalation leads to dearomatized products. C(sp3)? H bond activation occurs at ortho and para situated methyl groups. Steric shielding of the 4‐position in pyridine yields the ring‐metalated product through C(sp2)? H bond activation instead. The isolated compounds [Ca(2‐CH2‐C5H4N)2(THF)] ( 2 b ?(THF)), [Ca(4‐CH2‐C5H4N)2(THF)2] ( 3 b ?(THF)2), [Ca(2‐CH2‐C5H3N‐6‐CH3)2(THF)n] ( 4 b ?(THF)n; n=0, 0.75), [Ca{2‐C5H3N‐4‐C(CH3)3}2(THF)2] ( 5 c ?(THF)2), [Ca{4,4′‐(C3H5)2‐(C10H8N2)}(THF)] ( 6 a ?(THF)), [Ca(NC13H9‐9‐C3H5)2(THF)] ( 7 a ?(THF)), [Ca(4‐C3H5‐C9H7N)2(THF)] ( 8 b ?(THF)), and [Ca(1‐C3H5‐C9H7N)2(THF)3] ( 9 a ?(THF)3) have been characterized by NMR spectroscopy and metal analysis. 9 a ?(THF)4 and 4 b ?(THF)3 were additionally characterized in the solid state by X‐ray diffraction experiments. 4 b ?(THF)3 shows an aza‐allyl coordination mode in the solid state. Based on the results, mechanistic aspects are discussed in the context of previous findings.  相似文献   

3.
Reduction of [(C5H5)CoI2]2 by sodium amalgam in toluene in the presence of 1,3-butadiene, 1,3-cyclohexadiene or 1,5-cyclooctadiene affords the corresponding cyclopentadienylcobalt(I) diolefin complexes in high yields. Reduction of [(C5H5)CoI2]2 in the presence of 2-butyne yields the binuclear metallocyclic compound (C5H5)2Co2(C4(CH3)4), previously characterized as a structurally fluxional catalyst for alkyne cyclotrimerisation, as the major product; a trinuclear dicarbyne compound, (C5H5)3Co3(C-CH3)2, is obtained as a minor product. With diphenylacetylene, the analogous phenylcarbyne derivative (C5H5)3Co3(C-C6H5)2, previously obtained from thermal reaction with (C5H5)Co(CO)2, is obtained along with the major product, the tetraphenylcyclobutadiene complex (C5H5)Co(C4(C6H5)4). Pathways and intermediates for these reactions are discussed.  相似文献   

4.
The electron impact mass spectra of 1-sulfonyl substituted derivatives of 5-fluorouracil were investigated. The substituents were CH3SO2 (compound I), CH3(CH2)3SO2 (II), C6H5SO2 (III) and p-CH3C6H4SO2 (IV).  相似文献   

5.
Toxicity, antitumour, platinum distribution, hepatotoxicity and histology data are presented for a series of ferrocenylamines: [(η‐C5H4(CH2)nNH2)FeCp] (n = 0,1) ( 1 , 2 ); [(η‐C5H4CH2NHPh)FeCp] ( 3 ); [(η‐C5H4CH2NMe2)FeCp] ( 4 ); {[η‐C5H4CH(Me)NMe2]FeCp} ( 5 ); [η‐C5H4CH2NMe2)2Fe] ( 6 ); {[1,2η‐C5H3(CHMeNMe2)(PPh2)]FeCp} ( 7 ); {[1,2η‐C5H3(CHMeNMe2)(PPh2)]Fe[η‐C5H4PPh2]} ( 8 ); and their complexes cis‐PtCl2L2 ( 9 ); trans ‐ Pt(L)(dmso)X2 ( 10 ); [σ ‐ (L)Pt(dmso)X] ( 11 , 12 ) {σ‐(L)[Pt(dmso)X]2} ( 13 ); [σ‐(L)PtP(OPh)3Cl] ( 14 ) (L = ferrocenylamine). The toxicity order is 1 – 3 ≫ 4 – 8 for the ferrocenylamines; the lower toxicity of tertiary amines may be due to protonation in vivo. Pt(II) complexes all show increased toxicity over the ligand. Liver, not kidney, damage is the norm from i.p. injection of 1 – 14 and detailed platinum distribution, blood serum and histology studies with 9 and 11 show that the platinum distribution does not correlate with liver dysfunction. Complexes 9 – 14 , but not 1 – 8 , were active against P‐388 mouse leukaemia tumour and cisplatin‐resistant sarcoma, but inactive against L‐1210 mouse leukaemia and B‐16 melanoma. Copyright © 1999 John Wiley & Sons, Ltd.  相似文献   

6.
Dissociative ionisation of organometallic cyclopentadiene derivatives containing one, two or three M(CH3)3 groups (M  Si, Ge, Sn) has been studied.Among the monometallated compounds, C5H5Si(CH3)2Cl, C5H5Si(CH3)2OCH3 and (C5H5)4Sb have also been investigated. To verify fragmentation patterns, the spectra of deuterated compounds such as C5D5Si(CH3)3, C5D5Sn(CH3)3, C5D4Si2(CH3)6 and C5D3Si3)9 have been measured. Dissociative ionisation of h1-cyclopentadienyl derivatives has been shown to differ essentially from that of h5-compounds.  相似文献   

7.
The dinuclear cobalt complex [CH2(C5H4)2][Co(PMe3)2]2 (2), which is prepared from CoCl(PMe3)3 and [CH2(C5H4)2]Li2, reacts with NH4PF6 and CH3I to form the protonated and methylated dications {[CH2(C5H4)2][CoR(PMe3)2]2}2+ (R = H, CH3). Treatment of {[CH2(C5H4)2][CoCH3(PMe3)2]2}I2 (4) with LiCH3 affords the neutral compound [CH2(C5H4)2][Co(CH3)2(PMe3)]2 (5). Ligand substitution of [CH2(C5H4)2][Co(CO)2]2 (6) with P2Me4 and 1,2-C2H4(PMe2)2(dmpe) gives the doubly-bridged complexes [CH2(C5H4)2][Co2(CO)2(μ-P2Me4)] (7) and [CH2(C5H4)2][Co2(CO)2(μ-dmpe)] (8), respectively. Similarly, [CH2(C5H4)2][Co-(CO)(PMe3)]2 (9) is obtained from the reaction of 6 with PMe3. Oxidation of 6 with iodine gives [CH2(C5H4)2][Co(CO)I2]2 (11) which is transformed via {[CH2(C5H4)2][Co(PMe2H)3]2}I4 (12) into the triply-bridged cobalt(II) complex [CH2(C5H4)2][CO2(μ-PMe2)2] (13).  相似文献   

8.
The positive-ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC5H4CH2Fe(CO)2C5H5, NC5H4CH2COMo(CO)2C5H5, NC5H4CH2W(CO)3C5H5, NC5H4CH2COMn(CO)4, C5H10NCH2CH2Fe(CO)2C5H5, (CH3)2NCH2CH2COFeCOC5H5 and (CH3)2NCH2CH2COMn(CO)4 obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C5H5Mo(CO)3CH2NCO; (iii) The arylazomolybdenum derivatives RN2Mo(CO)2C5H5 (R ? phenyl, p-tolyl, or p-anisyl); (iv) The compound (C6H5N)2COFe2(CO)6 obtained from Fe3(CO)12 and phenyl isocyanate; (v) The N,N,N′,N′-tetramethylethylenediamine complex (CH3)2NCH2CH2N(CH3)2W(CO)4. Further examples of eliminations of hydrogen, CO, and C2H2 fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC5H4CH2MC5H5]+ to give the ions [(C5H5)2M]+ (M ? Fe, Mo and W); (ii) Conversion of C5H5Mo(CO)3CH2NCO to C5H5Mo(CO)2CH2NCO within the mass spectrometer; (iii) Elimination of N2 from [RN2MoC5H5]+ to give [RMoC5H5]+; (iv) Novel eliminations of HNCO, FeNCO, and C6H5NC fragments in the mass spectrum of (C6H5N)2COFe2(CO)6; (v) Facile dehydrogenation of the N,N,N′,-N′-tetramethylethylenediamine ligand in the complex (CH3)2NCH2CH2N(CH3)2W(CO)4.  相似文献   

9.
The reaction of [Fe(π-C5H5)(CO)2]2 with the dialkyl disulphides R2S2 (R = CH3, C2H5, t-C4H9 or CH2C6H5) affords, as well as dinuclear derivatives of the type [Fe(π-C5H5)(CO)SR]2, trinuclear species of formula [Fe3(π-C5H5)3(CO)2(S)SR].  相似文献   

10.
The preparation of the compound CH3(C5H5)TIX [where X = OCOCH3, OCOC2H5, OCO-i-C3H7, tropolonate and 4-isopropyltropolonate] is described and their chemical behaviours as well as their PMR and IR spectra are discussed.  相似文献   

11.
The acid–base reaction between Y(CH2SiMe3)3(thf)2 and the pyridyl‐functionalized cyclopentadienyl (Cp) ligand C5Me4H? C5H4N (1 equiv) at 0 °C afforded a mixture of two products: (η5:κ‐C5Me4? C5H4N)Y(CH2SiMe3)2(thf) ( 1 a ) and (η5:κ‐C5Me4? C5H4N)2YCH2SiMe3 ( 1 b ), in a 5:2 ratio. Addition of the same ligand (2 equiv) to Y(CH2SiMe3)3(thf)2, however, generated 1 b together with the novel complex 1 c , the first well defined yttrium mono(alkyl) complex (η5:κ‐C5Me4? C5H4N)[C5HMe33‐CH2)‐C5H4N‐κ]Y(CH2SiMe3) containing a rare κ/η3‐allylic coordination mode in which the C? H bond activation occurs unexpectedly with the allylic methyl group rather than conventionally on Cp ring. If the central metal was changed to lutetium, the equimolar reaction between Lu(CH2SiMe3)3(thf)2 and C5Me4H? C5H4N exclusively afforded the bis(alkyl) product (η5:κ‐C5Me4? C5H4N)Lu(CH2SiMe3)2(thf) ( 2 a ). Similarly, the reaction between the ligand (2 equiv) and Lu(CH2SiMe3)3(thf)2 gave the mono(alkyl) complex (η5:κ‐C5Me4? C5H4N)2LuCH2SiMe3 ( 2 b ), in which no ligand redistribution was observed. Strikingly, treatment of Sc(CH2SiMe3)3(thf)2 with C5Me4H? C5H4N in either 1:1 or 1:2 ratio at 0 °C generated the first cyclopentadienide‐based scandium zwitterionic “tuck‐over” complex 3 , (η5:κ‐C5Me4? C5H4N)Sc(thf)[μ‐η51:κ‐C5Me3(CH2)‐C5H4N]Sc(CH2SiMe3)3. In the zwitterion, the dianionic ligand [C5Me3(CH2)‐C5H4N]2? binds both to Sc13+ and to Sc23+, in η5 and η1/κ modes. In addition, the reaction chemistry, the molecular structures, and the mechanism are also discussed in detail.  相似文献   

12.
A number of carbene complexes of formulas Cl3GeMn(CO)4C(OR′)R and C5H5Mo(CO)2(GeCl3)C(OR′)CH3 (R = CH3, C6H5; R′ = CH3, C2H5) have been prepared by the reaction of [N(C2H5)4]GeCl3 with CH3Mn(CO)5, C6H5Mn(CO)5, or C5H5Mo(CO)3CH3 followed by alkylation of the resulting trichlorogermylacylcarbonylmetallate ion. The compound C5H5Mo(CO)2(GeCl3)COCH2CH2CH2 has been prepared directly by the reaction of [N(C2H5)4]GeCl3 with C5H5Mo(CO)3(CH2)3Br.  相似文献   

13.
Photolysis of a solution of Cp*RuCp (1) in CF3CO2H generates salt [CpRu(C5Me4CH2)]-(O2CCF3)(2 • O2CCF3). The reaction of compound 1 with oleum at 20 °C through the intermediate dication [η5-(CH2C5Me4)Ru(μ:η55-C5H4C5H5)Ru(C5Me4CH2)-η6]2+ leads to the triply charged cation η7CH2)2C5Me3Ru(μη55-C5H4C5H4)Ru(C5Me4CH2)-η6]3+. Synthesis of pentamethylmetallocene derivatives CpMC5Me4X (M = Ru, Fe; X = CHO, CH2OH, CH2An) has been accomplished. The reactions of 1-hydroxymethyl-2,3,4,5-tetramethylruthenocene with acids CF3CO2H, HBF4, CF3CO2H/NaB[C6H3(CF3)2]4, and picric acid C6H2(NO2)3OH afforded salts 2•X (X = CF3CO2, BF4, B[C6H3(CF3)2]4), and (2,3,4,5-tetram ethylruthenocenyl)methyl picrate [CpRu(C5Me4CH2)-η6][(C6H2(NO2)3O] (2•C6H2(NO2)3O). Structure of the latter was characterized by single crystal X-ray diffraction.  相似文献   

14.
The ditertiary phosphines (C6H5)2P(CH2)nP(C6H5)2 (n = 1 and 2), cis(C6H5)2PC2H2P(C6H5)2 and (C6H5)2PN(C2H5)P(C6H52 and the ditertiary arsines (C6H5)2As(CH2)nAs(C6H5)2 (n = 1 and 2) react with [Fe(CO)3SC6H5]2 to give a wide range of products, the nature of which depends on the reaction conditions and the ligand involved. Examples of the different types of comp isolated include, (i) Fe2(CO)5[(C6H5)2PCH2P(C6H5)2](SC6H5)2, in which the ligand acts as a monodentate, (ii) {[Fe(CO)2SC6H5]2[(C6H5)2PC2H4P(C6H5)2]}2, in which two [Fe(CO)2SC6H5]2 moieties are bridged by two diphosphine ligands, (iii) [Fe(CO)2SC6H5]2[(C6H5)2PN(C2H5)P(C6H5)2], in which the ligand bridges the two iron atoms, and (iv) Fe(CO)3(SC6H5)2Fe(CO)[(C6H5)2PC2H2P(C6H5)2], which contains the ligand chelated to a single iron atom. The tertiary phosphines PR3 (R=C2H5 and C6H5), phosphites P(OR′)3(R′ = CH3, C2H5, i-C3H7 and C6H5) and the stibine Sb(C6H5)3 bring about mono-, bis- or tris-substitution in [Fe(CO)3SC6H5]2 depending on the reaction conditions and the ligand involved. Whereas in solution [Fe(CO)2L(SC6H5)]2 [L = PR3 (R = C2H5 and C6H5), P(OC6H5)3 and Sb(C6H5)3] exist as a single isomer, [Fe(CO)2L′(SC6H5)]2 [L′=P(OR′)3 (R'=CH3, C2H5 and i-C3H7)] occur as a mixture of isomers.  相似文献   

15.
The tertiary phosphine π-C5H5Fe(CO)2P(C6H5)2 reacts with a suspension of Fe2(CO)9 in benzene to give the dinuclear complex π-C5H5Fe2P(C6H5)2(CO)6. This compound is also obtained by nucleophilic attack of [π-C5H5Fe(CO)2] on Fe(CO)4-[P(C6H5)2Cl] in tetrahydrofuran. Irradiation of a benzene solution of π-C5H5Fe2-P(C6H5)2(CO)6 with ultraviolet light affords π-C5H5Fe2P(C6H5)2(CO)5 which contains both a bridging carbonyl and a bridging phosphido group. The unstable bridged sulphido derivatives π-C5H5Fe2SR(CO)6 (R = CH3 and C6H5) and π-C5H5Fe2(t-C4H9S)(CO)5 are similarly obtained employing π-C5H5Fe(CO)2SR as ligand. The reactions of π-C5H5Fe2P(C6H5)2(CO)5 with tertiary phosphines and phosphites yield three types of products depending on the reaction conditions and the ligand involved. Examples include π-C5H5Fe2P(C6H5)2(CO)4P(C6H5)3, a mono-substituted derivative of π-C5H5Fe2P(C6H5)2(CO)5, and π-C5H5Fe2P(C6H5)2(CO)5P(C2H5)3 and π-C5H5Fe2P(C6H5)2(CO)4[P(OCH)3)3]2, mono- and bis-substituted derivatives of π-C5H5Fe2P(C6H5)2(CO)6, respectively. The reaction of π-C5H5Fe2P(C6H52(CO)5 with (C6H5)2PCH2P(C6H5)2 in benzene under reflux affords [π-C5H5Fe2P(C6H5)2(CO)4](C6H5)2PCH2P(C6H5)2 in which the ditertiary phosphine bridges two iron atoms.  相似文献   

16.
The mass spectra of the following acetylenic derivatives of iron, ruthenium and osmium carbonyls are reported: the iron compounds Fe2(CO)6[C2(C6H5)s2]2, Fe2(CO)6[C2(CH3)2]2 and Fe2(CO)6[C2(C2H5)2]2, the ruthenium compounds Ru2(CO)6[C2(C6H5)2]2, and Ru2(CO)6[C2(CH3)2]2 and the osmium compounds Os2(CO)6[C2(C6H5)2]2, Os2(CO)6[C2HC6H5]2 and Os2(CO)6[C2(CH3)2]2. Iron compounds exhibit breakdown schemes where binuclear, mononuclear and hydrocarbon ions are present. On the other hand, ruthenium and osmium compounds fragment in a similar way and give rise to singly and doubly charged binuclear ions. Phenylic derivatives of ruthenium and osmium also give weak triply charged ions. The results are discussed in terms of relative strengths of the metal-metal and metal-carbon bonds.  相似文献   

17.
The preparation of (borinato)(cyclobutadiene)cobalt complexes from the reactions of Co(C5H5BR)(1,5-C8H12) with acetylenes C2R′2 and of [C4(CH3)4]Co(CO)2I with Tl(C5H5BR) (R,R′ = CH3, C6H5) is described.In electrophilic substitution reactions Co(C5H5BCH3)[C4(CH3)4] (IVa) is more reactive than ferrocene. CF3CO2D effects H/D-exchange in the α-position of the borabenzene ring within a few minutes at ambient temperature and in the γ-position within less than four hours Friedel-Crafts acetylation with CH3COCl/AsCl3 in CH2Cl2 affords the 2-acetyl and the 2,6-diacetyl derivative of IVa. With the more active catalyst AlCl3, ring-member substitution is effected to give cations [Co(arene)C4(CH3)4]+ (arene = C6H5CH3, 2-CH3C6H4COCH3). Vilsmeier formylation gives the 2-formyl derivative of IVa. The acyl derivatives Co(2-R1CO-6-R2C5H3BCH3)[C4(CH3)4] (R1 = CH3, R2 = H, CH3CO and R1 = R2 = H) transform to the corresponding cations [Co(ortho-R1R2C6H4)C4(CH3)4]+ in superacidic media. The mechanistic relationship between acylation and ring-member substitution is discussed in detail.  相似文献   

18.

Abstract  

Reactions of the pyridyl side-chain-functionalized cyclopentadiene [C5H5CR2(CH2C5H4N)] [R 2 = Et2 (1), (CH2)4 (2)] with Ru3(CO)12 in refluxing xylene gave the new intramolecular C–H activated trinuclear product [μ-(C5H3N)CH2C(C2H5)2(C5H4)Ru(CO)]2Ru(CO)2 (3) and the normal dinuclear metal complex [(C5H4N)CH2C(CH2)4(C5H4)Ru(CO)]2(μ-CO)2 (4). The structures of the trinuclear complex 3 and dinuclear complex 4 were characterized by elemental analysis, IR spectra, 1H-NMR and X-ray diffraction.  相似文献   

19.
The compound Mo(η-C5H4(CH2)2SPrn)2(SPrn)2 acts as a bidentate ligand giving the heteronuclear bi-metallic compounds [Mo(η-C5H4CH2CH2SPrn)2-(SPrn)2(PtCl2)],[Mo(η-C5H4CH2CH2SPrn)2(SPrn)2(PdCl2)2], [Mo(η-C5C4CH2CH2SPrn)2(SPrn)2(RhCl3)2], [Mo(η-C5H4CH2CH2SPrn)2(μ-SPrn)2Rh(dppe)]BF4, [Mo(η-C5H4CH2CH2SPrn)2(μ-SPrn)2(COD)Rh]Cl, [Mo(η-C5H4CH2CH2SPrn)2-(μ-SPrn)2Pt(PPh3)2](PF6)2, and the compound [Mo(η-C5H4(CH2)2-μ-SPh)2Cl2Rh(COD)]Cl bonds via the ring-sulphur substituents giving [Mo(η-C5H4(CH2)2-μ-SPh)2-Cl2Rh(COD)]Cl.  相似文献   

20.
Two benzene centered tri- and tetracyclopentadienyl ligands C6H3(CH2C5H5)3-1,3,5 (1) and C6H2(CH2C5H5)4-1,2,4,5 (2) and their titanium complexes C6H3[CH2C5H4Ti(C5H5)Cl2]3-1,3,5 (3), C6H3[CH2C5H4Ti(C5H4CH3)Cl2]3-1,3,5 (4), as well as C6H2[CH2C5H4Ti(C5H5)Cl2]4-1,2,4,5 (5) were synthesized and characterized by mass and 1H NMR spectra. In the presence of methylaluminoxane (MAO), 3, 4 and 5 are efficient catalysts for ethylene polymerization in toluene. The influence of the polymerization conditions such as catalyst concentration, MAO/Ti molar ratio, polymerization time and temperature were investigated in detail. 3, 4 and 5 produce linear polyethylene (PE) with broad molecular weight distributions (MWD) and a little lower molecular weight.  相似文献   

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