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1.
The chiral bis-imine (1 R,2 R)-C 6H 10-[ E---N=CH---C 6H 3---3,4-(OMe) 2] 2 1 (LH) reacts with [Pd(OAc) 2] (1:1 molar ratio; OAc=acetate) giving the orthometallated [Pd(OAc)( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)-C 6H 10--- N=CH---C 6H 3-3′,4′-(OMe) 2-κ-C,N,N)] 2 (abbreviated as [Pd(OAc)(L-κ-C,N,N)]), through C---H bond activation on only one of the aryl rings and N, N-coordination of the two iminic N atoms. 2 reacts with an excess of LiCl to give [Pd(Cl)(L-κ-C,N,N)] 3. The reaction of 3 with AgClO 4 and neutral or anionic ligands L′ (1:1:1 molar ratio) affords [Pd(L-κ-C,N,N)(L′)](ClO 4) (L′=PPh 3 4a, NCMe 5, pyridine 6, p-nitroaniline 7) or [Pd(I)(L-κ-C,N,N)] 8. Complex 4a reacts with wet CDCl 3 giving [Pd( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)---C 6H 10--- NH 2-κ-C,N,N)(PPh 3)](ClO 4) 4b as a result of the hydrolysis of the C=N bond not involved in the orthometallated ring. The molecular structure of 4b·CH 2Cl 2 has been determined by X-ray diffraction methods. Cleavage of the Pd---N bond trans to the C aryl atom can be accomplished by coordination of strongly chelating ligands, such as acetylacetonate (acac) or bis(diphenylphosphino)ethane (dppe), forming [Pd(acac- O, O′)(L-κ-C,N)] 9 and [Pd(L-κ-C,N)(dppe-P,P′)](ClO 4) 12, while classical N, N′-chelating ligands such as 1,10-phenantroline (phen) or 2,2′-bipyridyl (bipy) behave as monodentate N-donor ligands yielding [Pd(L-κ-C,N,N)(κ 1-N-phen)](ClO 4) 10 and [Pd(L-κ-C,N,N)(κ 1-N-bipy)](ClO 4) 11. Treatment of 1 with PtCl 2(DMSO) 2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives Cl 2Pt[( NH 2) 2C 6H 10---N,N′] 13a and [Pt(Cl)( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)---C 6H 10--- NH 2-κ-C,N,N)] 13b, while [Pt(Cl)(L-κ-C,N,N)] 14 can be obtained by reaction of [Pt(μ-Cl)(η 3-2-Me---C 3H 4)] 2 with 1 in refluxing CHCl 3. Complexes 2 and 3 catalyzed the arylation of methyl acrylate giving good yields of the corresponding methyl cinnamates and TON up to 847 000. Complex 3 also catalyzes the hydroarylation of 2-norbornene, but with lower yields and without enantioselectivity. 相似文献
2.
The behaviour of tetraarylstannanes, R 4Sn (R = C 6H 5CH 2, C 6H 5, o-, m-, p-CH 3C 6H 4), towards SO 2 under various conditions has now been studied in detail. Compared to aliphatic tetraorganostannanes, the variability of the reaction products is much less, so that in nearly all cases only disulfinates, R 2Sn(O 2SR) 2, are formed. The aromatic tin(IV) mono-, di- and tri-sulfinates are also obtained by metathetical reaction between the corresponding organotin halides and sodium sulfinates. A unique feature of triaryltin chlorides, R 3SnCl (R = C 6H 5, o-, m-, p-CH 3C 6H 4), is their disproportionation in liquid SO 2 leading to disulfinates, R 2Sn(O 2SR) 2, and dichlorides, R 2SnCl 2. ( p-CH 3C 6H 4) 2SnCl 2, under more efficient conditions, also accepts SO 2 forming ( p-CH 3C 6H 4SO 2) 2SnCl 2. The structural investigations of the newly prepared compounds are carried out on the basis of their IR and 1H NMR spectra. 相似文献
3.
The complexes [(η 6-arene)Ru=C(OMe)CH 2R′)Cl(PR 3)]PF 6 (R′ = Ph; ARENE = Me 4C 6H 2, iPr 3C 6H 3, Et 3C 6H 3; PR 3 = PMe 3, PPh 3, P(OMe) 3) have been made from RuCl 2(PR 3)(arene) precursors by activation at room temperature of phenylacetylene in methanol containing NaPF 6. The complex with R′ = nBu, ARENE = Me 4C 6H 2, and PR 3 = PMe 3 is similarly formed from hex-1-yne but much more slowly, and a complex of the type [( p-cymene)Ru=C(OMe)CH 2R′)Cl(PR 3)] +PF 6− could be obtained only when the phosphine was the bulky PPh 3 (10b). It has been shown that the steric hindrance by both arene and phosphine ligands contributes to the stabilization of the carbeneruthenium complexes. 相似文献
4.
The X-ray crystal structures of ( N, N′-bis-( o-amidobenzilidene)-1,3-diaminopropane)nickel (Niambpr), ( N, N′-bis-( o-amidobenzilidene)-1,4-diaminobutane)nickel (Niambut), ( N, N′-bis-( o-thiobenzilidene)-1,4-diaminobutane)nickel(II) (Nitsalbut), bis-acetonitrile-( N, N′-bis-( o-aminobenzyl)-1,2-diaminoethane) nickel(II) tetrafluoroborate [Ni(H 4amben)(MeCN) 2] [BF 4] 2, bis- O-acetato-( N, N′-bis-( o-aminobenzyl)-1,2-diaminoethane) nickel(II) [Ni(H 4amben)(OAc) 2 · H 2O] and bis- O-acetato-( N, N′-bis-( o-aminobenzyl)-1,3-diaminopropane) nickel(II) [Ni(H 4ambpr)(OAc) 2] are presented. These structures complete the structural characterisation of the simple unsubstituted Schiff’s base complexes with N 4 and N 2S 2 donor sets and allow us to assess the effects of donor groups and polymethylene chain length on the coordination geometries of nickel(II). The hydrogenated N 4 complexes offer an insight into the effects of increased flexibility and character of the internal nitrogen donors. Unlike the parent N 4 imine species the hydrogenated amine species do not deprotonate at the peripheral nitrogen donors and do not seem to be restricted to the meridial plane of the nickel. 相似文献
5.
The catalytic properties of a series of Fe(II) diimine complexes (diimine= N, N′- o-phenylenebis(salicylideneaminato), N, N′-ethylenebis(salicylideneaminato), N, N′- o-phenylenebisbenzal, N, N′-ethylenebisbenzal) in combination with ethylaluminoxane (EAO) for ethylene oligomerization have been investigated. Treatment of the iron(II) complexes with EAO in toluene generates active catalytic systems in situ that oligomerize ethylene to low-carbon olefins. The effects of reaction temperature, ratios of Al/Fe and reaction periods on catalytic activity and product distribution have been studied. The activity of complex FeCl 2(PhCH= o-NC 6H 4N=CHPh) with EAO at 200°C is 1.35×10 5 g oligomers/mol Fe·h, and the selectivity of C 4–10 olefins is 84.8%. 相似文献
6.
An investigation of the frontier molecular orbitais of o- and p-RC 6H 4NC (R=H, CH 3, NO 2, F, Cl, CF 3, OCH 3) was carried out so that a thorough understanding of the intricacies of σ donation and π acceptance could be developed and used to modify subtly the electron density on metal centers. The results of this study-Indicate that the substituent position (ortho vs. para ) does alter the electron density in the ligand appreciably and that substitution of the phenyl ring with the groups indicated has a smaller effect on the σ-donating ability than it does on the π-accepting ability of the isonitrile ligand. The π-accepting abilities of the isonitrile ligands increase in the order o-, p-CH3OC6H4NC, o-, p-CH3C6H4NC, o-, p-C6H5NC, o-, p-FC6H4NC, o-, p-CF3C6NC, o-, p-ClC6H4NC, o-, p-NO2C6H4NC while the σ-donating ability decreases in this order. The energies of the σ-donor and π-acceptor orbitais are shown to correlate well with observed E
values of Cr(RC6H4NC)6 and Mn(RC6H4NC)6+1 complexes. This demonstrates how the theoretical results can be useful in understanding the observed physical properties of isonitrile-metal complexes. 相似文献
7.
The new chloro(cyclopentadienyl)silanes Cp′SiH yCl 3−y (Cp′=Me 4EtC 5, y=1: 1; Cp′=Me 4C 5H, y=1: 2; y=0: 3; Cp′=Me 3C 5H 2, y=1: 4 and pentachloro(cyclopentadienyl)disilanes Cp′Si 2Cl 5 (Cp′=Me 5C 5 5, Me 4EtC 5 6, Me 4C 5H 7, Me 3C 5H 2 8, Me 3SiC 5H 4 9) are synthesized in good yields via metathesis reactions. Treatment of 1–9 with LiAlH 4 leads under Cl–H exchange to the hydridosilyl compounds Cp′SiH 3 (Cp′=Me 4EtC 5 10, Me 4C 5H 11, Me 3C 5H 2 12) and to the hydridodisilanyl compounds Cp′Si 2H 5 (Cp′=Me 5C 5 13, Me 4EtC 5 14, Me 4C 5H 15, Me 3C 5H 2 16, Me 3SiC 5H 4 17). Complexes 1–17 are characterized by 1H, 13C, and 29Si-NMR spectroscopy, IR spectroscopy, mass spectrometry and CH-analysis. The structures of 6, 7 and 9 are determined by single-crystal X-ray diffraction analysis. Pyrolysis studies of the cyclopentadienylsilanes 10–12 and disilanes 13–17 show their suitability as precursors in the MOCVD process. 相似文献
8.
The aryldiazenido ligands provide the fourth member of the isoelectronic series CO, NO +, RNC, RN 2+ of ligands for transition metal complexes. The first aryldiazenido metal complex was reported in 1964 when p-CH 3OC 6H 4N 2Mo(CO) 2C 5H 5 was prepared by the reaction of NaMo(CO) 3C 5H 5 with p-CH 3OC 6H 4N 2+BF 4−. This review surveys the development of organometallic aryldiazenido chemistry since that time. Such organometallic aryldiazenido derivatives, including RN 2M(CO) 2C 5H 5, RN 2M(CO) 2(Pz 3BH) (M = Cr, Mo, W), [(η 6-Me 6C 6)Cr(CO) 2N 2Ar] +, [(MeC 15H 4)M′(CO) 2N 2Ar] + M′ = Mn, Re), [ trans-PhN 2Fe(CO) 2(PPh 3) 2] +, and PhN 2M′(CO) 2(PPh 3) 2(PPh 3) 2 can be obtained by reactions of arenediazonium salts with suitably chosen transition metal nucleophiles. Analogous methods cannot be used to prepare alkyldiazenido transition metal complexes because of the instability of alkyldiazonium salts. However, the alkyldiazenido derivatives RCH 2N 2M(CO) 2C 5H 5 (R = H or Me 3Si) can be obtained from HM(CO) 3C 5H 5 and the corresponding diazoalkanes. Important aspects of the chemical reactivity of RN 2M(CO) 2Q derivatives (Q = C 5H 5, Pz 3BH) include CO substitution reactions, coordination of the second nitrogen in the RN 2 ligand to give heterobimetallic complexes such as C 5H 5Mo(CO) 2(μ-NNC 6H 4Me)(CO) 2C 5H 5, oxidative addition rections with X 2 X = Cl, Br, I), SnX 4, RSSR, and CINO, and reactions with further RN 2+ to give bis(aryldiazenido) derivatives (RN 2) 2MQL + (L = CO, X −, etc.). Dearylation of an aryldiazenido ligand to a dinitrogen ligand can be effected by reaction of [(MeC 5H 4)M′(CO) 2N 2Ar] + with certain nucleophiles to give (MeC 5H 4)M′(CO) 2N 2. 相似文献
9.
Some (η 5-cyclopentadienyl)(1,2-bis(diarylphosphino)ethane)(diorganosulfide)ruthenium complexes, [Ru(η 5-C 5H 5)(Ar 2PCH 2CH 2-PAr 2)(R 1R 2S)]BF 4 (Ar = Ph, p-Tol; R 1, R 2 = Ph, Et) were prepared. Variable temperature NMR spectra of these complexes showed the existence of two fluxional processes; inversion at the sulfur atom and δ-λ interconversion of the chelate ring. The former process was slower, and its barriers in these complexes were calculated as ca. 7 kcal mol −1. The spectral features of ethyl phenyl sulfide complexes suggested that substantiation of the new chiral center at sulfur induces a significant conformational rigidity at the chelate ring. 相似文献
10.
LnCl 3 (Ln=Nd, Gd) reacts with C 5H 9C 5H 4Na (or K 2C 8H 8) in THF (C 5H 9C 5H 4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C 5H 9C 5H 4)LnCl 2(THF) n (orC 8H 8)LnCl 2(THF) n], which further reacts with K 2C 8H 8 (or C 5H 9C 5H 4Na) in THF to form the litle complexes. If Ln=Nd the complex (C 8H 8)Nd(C 5H 9C 5H 4)(THF) 2 (a) was obtained: when Ln=Gd the 1 : 1 complex [(C 8H 8)Gd(C %H 9)(THF)][(C 8H 8)Gd(C 5H 9H 4)(THF) 2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). 相似文献
11.
The reaction of [Nb(η 5-C 5H 4R) 2X 2] [1: R = SiMe 3, X = Cl; 2: R = SiMe 3, X = Br; 3: R = H, X = Cl; 4: R = t, X = Cl] with nitroso derivatives ArNO [ a: Ar = Ph; b: Ar = o-CH 3-C 3H 4; c: Ar = p-(CH 3) 2NC 6H 4] yields paramagnetic complexes formulated as [Nb(η 5-C 5H 4R)(η 3-C 5H 4R)X 2(ArNO- N, O) 1a, 1b, 1c, 2a, 3a, 4a and 4c, which have been characterized by ESR and IR spectroscopy. 相似文献
12.
Reactions of [(η 6-arene)RuCl 2] 2 (1) (η 6-arene= p-cymene (1a), 1,3,5-Me 3C 6H 3 (1b), 1,2,3-Me 3C 6H 3 (1c) 1,2,3,4-Me 4C 6H 2(1d), 1,2,3,5-Me 4C 6H 2 (1e) and C 6Me 6 (1f)) or [Cp*MCl 2] 2 (M=Rh (2), Ir (3); Cp*=C 5Me 5) with 4-isocyanoazobenzene (RNC) and 4,4′-diisocyanoazobenzene (CN–R–NC) gave mononuclear and dinuclear complexes, [(η 6-arene)Ru(CNC 6H 4N=NC 6H 5)Cl 2] (4a–f), [Cp*M(CNC 6H 4N=NC 6H 5)Cl 2] (5: M=Rh; 6: M=Ir) , [{(η 6-arene)RuCl 2} 2{μ-CNC 6H 4N=NC 6H 4NC}] (8a–f) and [(Cp*MCl 2) 2(μ-CNC 6H 4N=NC 6H 4NC)}] (9: M=Rh; 10: M=Ir) , respectively. It was confirmed by X-ray analyses of 4a and 5 that these complexes have trans-forms for the ---N=N--- moieties. Reaction of [Cp*Rh(dppf)(MeCN)](PF 6) 2 (dppf=1,1′-bis (diphenylphosphino)ferrocene) with 4-isocyanoazobenzene gave [Cp*Rh(dppf)(CNC 6H 4N=NC 6H 5)](PF 6) 2 (7), confirmed by X-ray analysis. Complex 8b reacted with Ag(CF 3SO 3), giving a rectangular tetranuclear complex 11b, [{(η 6-1,3,5-Me 3C 6H 3)Ru(μ-Cl} 4(μ-CNC 6H 4N=NC 6H 4NC) 2](CF 3SO 3) 4 bridged by four Cl atoms and two μ-diisocyanoazobenzene ligands. Photochemical reactions of the ruthenium complexes (4 and 8) led to the decomposition of the complexes, whereas those of 5, 7, 9 and 10 underwent a trans-to- cis isomerization. In the electrochemical reactions the reductive waves about −1.50 V for 4 and −1.44 V for 8 are due to the reduction of azo group, [---N=N---]→[---N=N---] 2−. The irreversible oxidative waves at ca. 0.87 V for the 4 and at ca. 0.85 V for 8 came from the oxidation of Ru(II)→Ru(III). 相似文献
13.
合成并表征了含RCOO-基团的单核(Ni 1~Ni 2)及双核(Ni 3)镍配合物[(2,6-R 2-C 6H 3)—N=C(H)—(3-Ph-5-PhCOO-2-O-C 6H 2)- κ2-N, O]Ni(CH 3)(pyridine)](R= iPr;3,5- tBu 2C 6H 3),并用于催化乙烯均聚和共聚反应。 作为单组分催化剂,这些配合物可以有效地催化乙烯聚合得到中等相对分子质量的支化聚乙烯(PE)。 供电性的PhCOO—基团促进了催化剂Ni 1的引发,从而在低温下比Ni 0活性更高。 引入大位阻的2,6-(3,5-二叔丁基苯基)苯胺基团,催化剂Ni 2在5×10 5 Pa下的活性高达1.8×10 6 g PE mol -1·Ni -1·h -1,是活性最高的水杨醛亚胺中性镍催化剂之一。 与相应的单核催化剂相比,双核催化剂Ni 3对三苯基膦具有更好的耐受性。 这些催化剂可催化乙烯与1,5-己二烯、1,7-辛二烯、6-溴-1-己烯或10-十一烯酸甲酯的共聚合,制备功能化聚乙烯。 相似文献
14.
In the presence of methanesulfonic acid, the palladium(0)-olefin complexes: [Pd(η 2-ol)(P---N)] [ol=dimethyl fumarate or fumaronitrile, P---N=1-(Ph 2P)C 6H 4-2-CH=NR (R=CMe 3 or C 6H 4OMe-4)] catalyse the alkoxycarbonylation of terminal alkynes. Moderately good rates are obtained when the catalysts are promoted with two equivalents of the free P---N ligand and a large excess of acid at 120°C. The catalytic data suggest that derivatives of the type [Pd(alkyne)(P---N) n] ( n=2–3) are the active catalytic species. 相似文献
15.
The reactions of RNHSi(Me) 2Cl (1, R= t-Bu; 2, R=2,6-(Me 2CH) 2C 6H 3) with the carborane ligands, nido-1-Na(C 4H 8O)-2,3-(SiMe 3) 2-2,3-C 2B 4H 5 (3) and Li[ closo-1-R′-1,2-C 2B 10H 10] (4), produced two kinds of neutral ligand precursors, nido-5-[Si(Me) 2N(H)R]-2,3-(SiMe 3) 2-2,3-C 2B 4H 5, (5, R= t-Bu) and closo-1-R′-2-[Si(Me) 2N(H)R]-1,2-C 2B 10H 10 (6, R= t-Bu, R′=Ph; 7, R=2,6-(Me 2CH) 2C 6H 3, R′=H), in 85, 92, and 95% yields, respectively. Treatment of closo-2-[Si(Me) 2NH(2,6-(Me 2CH) 2C 6H 3)]-1,2-C 2B 10H 11 (7) with three equivalents of freshly cut sodium metal in the presence of naphthalene produced the corresponding cage-opened sodium salt of the “carbons apart” carborane trianion, [ nido-3-{Si(Me) 2N(2,6-(Me 2CH) 2C 6H 3)}-1,3-C 2B 10H 11] 3− (8) in almost quantitative yield. The reaction of the trianion, 8, with anhydrous MCl 4 (M=Ti and Zr) in 1:1 molar ratio in dry tetrahydrofuran (THF) at −78 °C, resulted in the formation of the corresponding half-sandwich neutral d 0-metallacarborane, closo-1-M[(Cl)(THF) n]-2-[1′-η 1σ-N(2,6-(Me 2CH) 2C 6H 3)(Me) 2Si]-2,4-η 6-C 2B 10H 11 (M=Ti (9), n=0; M=Zr (10), n=1) in 47 and 36% yields, respectively. All compounds were characterized by elemental analysis, 1H-, 11B-, and 13C-NMR spectra and IR spectra. The carborane ligand, 7, was also characterized by single crystal X-ray diffraction. Compound 7 crystallizes in the monoclinic space group P2 1/ c with a=8.2357(19) Å, b=28.686(7) Å, c=9.921(2) Å; β=93.482(4)°; V=2339.5(9) Å 3, and Z=4. The final refinements of 7 converged at R=0.0736; wR=0.1494; GOF=1.372 for observed reflections. 相似文献
16.
The reaction of the metallocene dichlorides Cp 2MCl 2 (Cp = η 5-C 5H 5; M = Ti, Zr, Hf, Mo, W) and Cp 2′TiCl 2 (Cp′ = η 5-C 5H 4CH 3) with equimolar amounts of dilithium-benzene- o-diselenolate, 1,2-(LiSe) 2C 6H 4, gives the chelate complexes Cp 2M(Se 2C 6H 4) (M = Ti (I), Zr (II), Hf (III), Mo (IV), W (V)) and Cp 2′Ti(Se 2C 6H 4) (VI). CpTiCl 3 reacts with 1,2-(LiSe) 2C 6H 4 to give CpTiCl(Se 2C 6H 4) (VII). The ring inversion activation parameters for I–VI can be determined by means of temperature-dependent 1H NMR spectroscopy in solution. The fragmentation behaviour of I–VII in the mass spectrometer has been investigated by pursuing metastable transitions, using linked-scan techniques. 相似文献
17.
Reductive dehalogenation of the (chloro)(phenylethynyl)phosphine (2,4,6- tBu 3C 6H 2O)(PhCC)PCl, I, by Co 2(CO) 8, II, yields the neutral phosphenium ion complex [(R)(R′)]P=Co(CO) 3, III, (R = 2,4,6- tBu 3C 6H 2O; R′ = (η 2-C≡CPh)Co 2(CO) 6), which contains a trigonally planar coordinated phosphorus atom. When NaCo(CO) 4, V, is used instead of II a dinuclear complex, Co 2(CO) 6[μ 2-P(R)(R′)] 2, VI, (R = 2,4,6- tBu 3C 6H 2O; R′ = C≡CPh) is formed in which the phosphido ligands P(R)(R′), bridge in a μ 2 fashion two Co(CO) 3 units. The mechanism of formation of VI, involving a formal dimerization of two [(2,4,6- tBu 3C 6H 2O)(PhC≡C)]P=Co(CO) 3 fragments, is discussed. However, ( tBu)(PhC≡C)PCl, VII, reacts with II, to yield the cluster compound VIII, containing the two μ 2-bridging units ( tBu)[(η 2-C≡CPh)Co 2(CO) 5]P and ( tBu)(PhC≡C)P. Compounds II and VI–VIII were identified from their analytical and spectroscopic (IR, 1H-, 13C- and 31P-NMR) data. The molecular structure of the cluster compound VIII was determined by an X-ray diffraction study. 相似文献
18.
The reaction of bidentate N,N-dimethylaniline-arylamido ligands,o-C6H4NMe2(CH2NHAr)(Ar =Ph,1a;2,6-Me2C6H3,1b; 2,6-Et2C6H3,1c; 2,6-ipr2C6H3,1d) with ZnEt2 yields the complexes o-C6H4(NMe2)(CH2NAr)ZnEt (2a-2d),respectively.All the complexes were characterized by 1H and 13C NMR spectroscopy and elemental analyses.It was found that all the zinc complexes were efficient catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol with good molecular weight control and narrow polydispersity. 相似文献
19.
The novel alkynyldithiocarboxylate complexes [Fe(η 5-C 5H 5)(S 2CCCR) (dppm-P)] (3a,b) and [Fe(η 5-C 5H 5)(S 2CCCR)(PPh 3)] (4a,b) were obtained through the insertion of CS 2 into the iron-akynyl bond in the complexes [Fe(η 5-C 5H 5)(CCR)(L)(L′] L, L′ = dppm R = Ph (1a), tBu(1b); L = (CO), L′ = (PPh 3) R = Ph (2a), tBu (2b). Variable-temperature 31P{ 1H} NMR studies indicate the presence of two different isomers, [Fe(η 5-C 5H 5)(η 3-S,C,S′---S 2CCCR)(L)(L′)] and [Fe(η 5-C 5H 5(η 2-S,S′-S 2CCCR)(L)(L′)], which rapidly interconvert at room temperature. The synthesis of the precursor complex [Fe(η 5-C 5H 5)(CC tBu)(CO)(PPh 3)] is also described. 相似文献
20.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
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