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1.
Cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4Hg)3 (1) is capable of reacting with ethanol to form a 1:1 complex, {[(o-C6F4Hg)3](EtOH)} (2), having a pyramidal structure. The ethanol molecule in 2 is coordinated through the oxygen atom to all Hg atoms of the macrocycle. The interaction of 1 with THF followed by drying of the product obtained in vacuum also gives the corresponding pyramidal 1:1 complex {[(o-C6F4Hg)3](THF)} (3). However, when a THF solution of 1 is slowly concentrated to a small volume and the resulting crystals are not dried, three cocrystallized adducts, viz., {[(o-C6F4Hg)3](THF)2} (4), {[(o-C6F4Hg)3](THF)3} (5) and {[(o-C6F4Hg)3](THF)4} (6), containing two, three and even four THF molecules, respectively, are produced. Complex 4 has a bipyramidal structure. Complexes 5 and 6 are also characterized by the presence of a bipyramidal fragment formed by two coordinated THF species. The topological analysis of the DFT-calculated function of the electron density distribution in the crystals of 2 and 3 revealed the critical points (3, −1) on each of the three Hg···O lines, which is in accord with the X-ray diffraction data indicating on the presence of the triply coordinated Lewis base molecule in both adducts. If a THF solution of 1 is held for a month at 20 °C on air under stirring, a sandwich complex of 1 with previously unknown bis-2,2′-tetrahydrofuryl peroxide (THFPO) is formed. The THFPO ligand in this sandwich, {[(o-C6F4Hg)3]2(THFPO)} (7), provides all its four oxygen atoms for the bonding to the molecules of 1. Two of these oxygen atoms, belonging to the tetrahydrofuryl moieties, are cooperatively bound each by three Hg atoms of the neighbouring macrocyclic unit whereas two others, belonging to the peroxide group, coordinate to a single Hg atom of the adjacent macrocycle.  相似文献   

2.
The reactions of three-mercury anticrown (o-C6F4Hg)3 (1) with acetoacetic ester (AE), malonic ester (ME), and malonodinitrile (MN) afford 1: 1 complexes {[(o-C6F4Hg)3](AE)} (3), {[(o-C6F4Hg)3](ME)} (4), and {[(o-C6F4Hg)3](MN)} (5). The structures of complexes 35 were determined by X-ray diffraction analysis. Complex 3 has a discrete structure in the solid state, whereas complexes 4 and 5 form in the crystal extended stacks representing polydecker sandwiches with alternating molecules of 1 and ME or MN. According to the X-ray diffraction and IR spectral data, the molecule of AE in complex 3 is in the keto form.  相似文献   

3.
As was shown by IR spectroscopy, the reaction of the three-mercury anticrown (o-C6F4Hg)3 (1) with the [H3BCN]ion in THF affords the complexes {[(o-C6F4Hg)3][H3BCN](5) and [(o-C6F4Hg)3]2[H3BCN](6). Complex 6 was isolated from solution in the analytically pure state. According to X-ray diffraction data, complex 6 has a double-decker sandwich structure, in which the borohydride group of the [H3BCN]? anion is bound to one anticrown molecule by three B-H-Hg bridges, whereas the cyanide group is cooperatively coordinated by three mercury centers of another molecule 1 through the nitrogen atom. The reaction of compound 1 with triethylamineborane Et3NBH3 in THF affords the 1: 1 complex ~[(o-C6F4Hg)3][Et3NBH3]~ (7). In this adduct, the binding of the aminoborane to the mercury anticrown is also accomplished by B-H-Hg bridges. The stability constants of complexes 5 and 6 in THF were determined.  相似文献   

4.
Cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4Hg)3 (1) is able to bind hexacyanoferrate(III) and nitroprusside anions to form complexes {[(o-C6F4Hg)3]2[Fe(CN)6]}3− and {[(o-C6F4Hg)3]2[Fe(CN)5NO]}2−, respectively, which contain one anionic species per two macrocycles. According to X-ray diffraction data, the complexes have unusual sandwich structures wherein the anionic guest is located between the planes of two molecules of 1 and is coordinated to each of these through two types of Fe-C-N-Hg bridges. One type is the simultaneous coordination of a cyanide ligand to all three Hg centres of the cycle. The other type is the coordination of a cyanide group to a single Hg atom of the macrocycle. In both types, the bonding of the anionic guest with the macrocyclic host is accomplished with the participation of π-electrons of the cyanide ligands. The synthesized compounds are the first examples of host-guest complexes of a macrocyclic multidentate Lewis acid with anionic metal complexes.  相似文献   

5.
The new mononuclear palladium(II) and platinum(II) [M(p-SC6F4(CF3))2(dppe)] complexes M = Pd 1a, Pt 2a; [M(o-SC6H4(CF3))2(dppe)] M = Pd 1d, Pt 2d as well as the previously known [M(SC6F5)2(dppe)] M = Pd 1b, Pt 2b and [M(p-SC6HF4)2(dppe)] M = Pd 1c, Pt 2c, have been used as metalloligands for the preparation of the heteroleptic bimetallic complexes [M2(μ-SRf)2(dppe)2](SO3CF3)2 M = Pd, Rf = p-C6F4(CF3) 3a, C6F53b, p-C6HF43c, o-C6H4(CF3) 3d; M = Pt, Rf = p-C6F4(CF3) 4a, C6F54b, p-C6HF44c and o-C6H4(CF3) 4d. Variable temperature 19F NMR experiments show that the fluorothiolate bridged bimetallic compounds are fluxional in solution whereas mononuclear complexes are not. The solid state X-ray diffraction structures of [Pd(p-SC6HF4)2(dppe)] (1c), [Pt(SC6F5)2(dppe)] (2b) and [Pt(o-SC6H4(CF3))2(dppe)] (2d) show square-planar coordination around the metal centers. The solid state molecular structure of the compound [Pt2(μ-o-SC6H4(CF3))2(dppe)2](SO3CF3)2 (4d), exhibit a planar [Pt2(μ-S)2] ring with the sulfur substituents in an anti configuration.  相似文献   

6.
Seven Schiff base adducts of organotin(IV), RSnLCl2, which L is o-vanillin-2-thiophenoylhydrazone, and R is n-C4H9 (1), Me (2), Ph (3), and [R2SnL], which L is o-vanillin-2-thiophenoylhydrazone, R is n-C4H9 (4), Me (5), Ph (6), PhCH2 (7) have been synthesized. Those products were characterized by elemental analysis, IR, 1H, 13C and 119Sn NMR spectra. The crystal and molecular structures of compounds 1, 4, and 6 have been determined by X-ray single crystal diffraction. In the crystal of compound 1 the tin atom is rendered six-coordinate in a distorted octahedral configuration by coordinating with the N atom of the Schiff base ligand, in compounds 4 and 6 the central tin atoms are five-coordinate in distorted trigonal-bipyramidal geometry and the comparison of the IR spectra reveal that disappearance of the bands assigned to carboxyl unambiguously conforms the ligand coordinate with the tin atom in enol form.  相似文献   

7.
Four half-sandwich ruthenium(II) complexes [(η6-C6H6)Ru(L1-O)][PF6] (1), [(η6-C6H6)Ru(L2-O)][PF6] (2), [(η6-C6H6)Ru(L3-O)][PF6] (3), [(η6-C6H6)Ru(L4-O)][PF6] (4a), and [(η6-C6H6)Ru(L4-O)][BPh4] (4b) [L1-OH, 4-nitro-6-{[(2′-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L2-OH, 2,4-di-tert-butyl-6-{[(2′-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L3-OH, 2,4-di-tert-butyl-6-{[2′-((pyridin-2-yl)benzylamino)methyl}-phenol; L4-OH, 2,4-di-tert-butyl-6-{[(2′-imethylaminoethyl)methylamino]methyl}-phenol (L4-OH)], supported by a systematically varied series of tridentate phenolate-based pyridylalkylamine and alkylamine ligands are reported. The molecular structures of 1-3, 4a, and 4b have been elucidated in solution using 1H NMR spectroscopy and of 1, 3, and 4b in the solid state by X-ray crystallography. Notably, due to coordination by the ligands the Ru center assumes a chiral center and in turn the central amine nitrogen also becomes chiral. The 1H NMR spectra exhibit only one set of signals, suggesting that the reaction is completely diastereoselective [1: SRu,SN/RRu,RN; 2: RRu,RN/SRu,SN; 3: SRu,RN/RRu,SN; 4b: SRu,RN/RRu,SN]. The crystal packing in 1 and 3 is stabilized by C-HO interactions, in 4b no meaningful secondary interactions are observed. From the standpoint of generating phenoxyl radical, as investigated by cyclic voltammetry (CV), complex 1 is redox-inactive in MeCN solution. However, 2, 3, and 4a generate a one-electron oxidized phenoxyl radical coordinated species [2]2+, [3]2+, and [4a]2+, respectively. The radical species are characterized by CV, UV-Vis, and EPR spectroscopy. The stability of the radical species has been determined by measuring the decay constant (UV-Vis spectroscopy).  相似文献   

8.
A series of titanium complexes [(Ar)NC(CF3)CHC(R)O]2TiCl2 (4b: Ar = -C6H4OMe(p), R = Ph; 4c: Ar = -C6H4Me(p), R = Ph; 4d: Ar = -C6H4Me(o), R = Ph; 4e: Ar = α-Naphthyl, R = Ph; 4f: Ar = -C6H5, R = t-Bu; 4g: Ar = -C6H4OMe(p); R = t-Bu; 4h: Ar = -C6H4Me(p); R = t-Bu; 4i: Ar = -C6H4Me(o); R = t-Bu) has been synthesized and characterized. X-ray crystal structures reveal that complexes 4b, 4c and 4h adopt distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4b-c and 4f-i are active catalysts for ethylene polymerization and ethylene/norbornene copolymerization, and produce high molecular weight polyethylenes and ethylene/norbornene alternating copolymers. In addition, the complex 4c/MMAO catalyst system exhibits the characteristics of a quasi-living copolymerization of ethylene and norbornene with narrow molecular weight distribution.  相似文献   

9.
A series of fluorinated bipyridine derivatives, (4,4′-bis(RfCH2OCH2)-2,2′-bpy) {Rf = n-C8F17 (1a), n-C9F19 (1b), n-C10F21 (1c), n-C11F23 (1d)} have been successfully synthesized using 4,4′-bis(bromomethylene)-2,2′-bpy and fluorinated alkoxides. Bpy 1a-d have been characterized by multi-nuclei (1H, 19F, and 13C) NMR, GC/MS and FTIR. The Cu complexes 2a-d could be generated in situ by stirring ligands 1a-d with CuBr·Me2S at room temperature, respectively. The 3-component systems 3c-d, CuBr·Me2S/Bpy (1c-d)/2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO), were successfully used to the aerobic oxidation of alcohols under the fluorous biphasic system (FBS). The resulting products from FBS could be easily recovered by two phase separation with high yields up to 8 runs (>90%). In order to avoid using the expensive fluorous solvents, systems 3a-d, CuBr·Me2S/Bpy (1a-d)/TEMPO, were also successfully shown to catalyze the aerobic alcohol oxidation under the thermomorphic condition (in C6H5Cl), and the yields of oxidation of 4-nitrobenzyl alcohol were close to 100% even after 8 runs. In particular, 3a was most effective under the thermomorphic mode in the chemoselectivity of aerobic oxidation of aliphatic primary alcohols to aldehydes without any overoxidized acids.  相似文献   

10.
Kai-Min Wu 《Tetrahedron》2005,61(41):9679-9687
Three pendant benzamidines [Ph-C(NC6H5)-{NH(CH2)2NMe2}] (1), [Ph-C(NC6H5)-{NH(CH2Py)}] (2) and [Ph-C(NC6H5)-{NH(o-C6H4)(oxazoline)}] (3) are described. Reactions of 1, 2 or 3 with one molar equivalent of Pd(OAc)2 in THF give the palladacyclic complexes [Ph-C{-NH(η1-C6H4)}{N(CH2)2NMe2}]Pd(OAc) (4), [Ph-C{-NH(η1-C6H4)}{N (CH2Py)}]Pd(OAc) (5) and [Ph-C{-NH(η1-C6H4)}{N(o-C6H4)(oxazoline)}]Pd(OAc) (6), respectively. Treatment of 4, 5 or 6 with excess of LiCl in chloroform affords [Ph-C{-NH(η1-C6H4)}{N(CH2)2NMe2}]PdCl (7), [Ph-C{-NH(η1-C6H4)}{N(CH2Py)}]PdCl (8) and [Ph-C{-NH(η1-C6H4)}{N(o-C6H4)(oxazoline)}]PdCl (9). The crystal and molecular structures are reported for compounds 1, 3, 5, 6 and 7. The application of these palladacyclic complexes to the Suzuki and Heck coupling reactions was examined.  相似文献   

11.
A series of novel amphiphilic ferrocenylimines and their cyclopalladated complexes of general formula [Fe(η5-C5H5)(η5-C5H4CR1NR2)] (R1=H, R2=C12H25-n4a, R1=H, R2=C16H33-n4b, R1=CH3, R2=C12H25-n4c, R1=CH3, R2=C16H33-n4d), [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)CR1NR2]}]2 (5a-d), [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)-CR1NR2]}(PPh3)] (6a-d), were prepared and characterized by 1H NMR, 13C NMR, 31P NMR, IR, HRMS, and elemental analysis. The crystal structures of 5c,d were determined by X-ray crystallography. These amphiphilic cyclopalladated complexes are thermally stable and insensitive to oxygen and moisture. The redox properties of 4a-d, 5a-d, 6a-d were also investigated using cyclic voltammetric technique. Compounds 5a-d, 6a-d displayed good activity in the Heck reaction of a variety of aryl halides with ethyl acrylate or styrene and the Suzuki-Miyaura cross-coupling reaction of aryl bromides with phenylboronic acid in bulk solution. They are also suitable for formation of Langmuir-Blodgett (LB) films.  相似文献   

12.
Reaction of Mo(CO)3(NCMe)3 and PPh2(o-C6H4)C(O)H (abbreviated as PCHO) at room temperature affords Mo(CO)2(η3-PCHO)2 (1), while compound 1 and the phosphine-imine complex Mo(CO)4(η2-PPh2(o-C6H4)CHNMe) (2) are obtained by using Mo(CO)3(η3-(MeNCH2)3) as the reactant. Thermal reaction of 1 with C60 products Mo(CO)2(η4-(PPh2(o-C6H4)CH)2)(η2-C60) (3) in low yield, apparently through coupling of the formyl moieties. The structures of 1 and 3 have been determined by an X-ray diffraction study. The two aldehyde groups of 1 and C60 ligand of 3 are coordinated to the molybdenum atom in a π-fashion.  相似文献   

13.
Three highly fluorinated bipyridine derivatives (4,4′-bis(RfCH2OCH2)-2,2′-bpy) {Rf=HCF2(CF2)7 (1a), n-C8F17 (1b), n-C10F21 (1c)} have been synthesized using 4,4′-bis(BrCH2)-2,2′-bpy and the corresponding fluorinated alkoxides. The fluorine contents of ligands 1a-c are 58.3, 59.8, and 62.3%, respectively. Despite its high fluorine content, the ligand 1a with a -CF2H polar terminal group is more soluble in organic solvents. The ligand 1b is a white solid and is still moderately soluble in CH2Cl2. The ligand 1c has a high fluorophilicity, the partition ratio being 42:1 for the n-C8F18/CH2Cl2 system. The reaction of ligands 1a-c with [PdCl2(CH3CN)2] results in the novel Pd complexes [PdCl2(4,4′-bis-(RfCH2OCH2)-2,2′-bpy)] where Rf=HCF2(CF2)7 (2a), n-C8F17 (2b), n-C10F21 (2c), respectively. The Pd complex 2b is a pale yellow solid, and has been tested unsatisfactorily for FBC. Insoluble in organic solvents, the Pd complex 2c dissolves only in fluorinated solvents, for instance FC77, which is mainly n-C8F18. The novel Pd complex 2c has been tested as a catalyst in Heck reactions under a fluorous biphasic catalysis condition. It was found that the Pd complex 2c, after an easy separation, keeps its catalytic activity (>90% yield), even after seven runs. The TGA studies indicate that the Pd complexes 2a-c are stable up to 330 °C.  相似文献   

14.
Reaction of the benzene-linked bis(pyrazolyl)methane ligands, 1,4-bis{bis(pyrazolyl)-methyl}benzene (L1) and 1,4-bis{bis(3-methylpyrazolyl)methyl}benzene (L2), with pentamethylcyclopentadienyl rhodium and iridium complexes [(η5-C5Me5)M(μ-Cl)Cl]2 (M = Rh and Ir) in the presence of NH4PF6 results under stoichiometric control in both, mono and dinuclear complexes, [(η5-C5Me5)RhCl(L)]+ {L = L1 (1); L2 (2)}, [(η5-C5Me5)IrCl(L)]+ {L = L1 (3); L2 (4)} and [{(η5-C5Me5)RhCl}2(μ-L)]2+ {L = L1 (5); L2 (6)}, [{(η5-C5Me5)IrCl}2(μ-L)]2+ {L = L1 (7); L2 (8)}. In contrast, reaction of arene ruthenium complexes [(η6­arene)Ru(μ-Cl)Cl]2 (arene = C6H6, p-iPrC6H4Me and C6Me6) with the same ligands (L1 or L2) gives only the dinuclear complexes [{(η6-C6H6)RuCl}2(μ-L)]2+ {L = L1 (9); L2 (10)}, [{(η6-p-iPrC6H4Me)RuCl}2(μ-L)]2+ {L = L1 (11); L2 (12)} and [{(η6-C6Me6)RuCl}2(μ-L)]2+ {L = L1 (13); L2 (14)}. All complexes were isolated as their hexafluorophosphate salts. The single-crystal X-ray crystal structure analyses of [7](PF6)2, [9](PF6)2 and [11](PF6)2 reveal a typical piano-stool geometry around the metal centers with six-membered metallo-cycle in which the 1,4-bis{bis(pyrazolyl)-methyl}benzene acts as a bis-bidentate chelating ligand.  相似文献   

15.
Two types of diorganotin(IV) complexes {[R2Sn(O2CC4H3N2)]2O}2 (R = n-octyl 1, 2-ClC6H4CH23, 2-FC6H4CH25, 4-FC6H4CH27) and R2Sn(O2CC4H3N2)2 (R = n-octyl 2, 2-ClC6H4CH24, 2-FC6H4CH26, 4-FC6H4CH28) were prepared by reactions of diorganotin oxide with 2-pyrazinecarboxylic acid. The complexes 1-8 are characterized by elemental analysis, IR and NMR (1H, 13C, 119Sn) spectroscopies. The complexes {[(n-C8H17)2Sn(O2CC4H3N2)]2O}2 (1) and (n-C8H17)2Sn(O2CC4H3N2)2 (2) are also determined by X-ray single crystal diffraction, which reveal that the endo-cyclic tin atom of complex 1, is seven-coordinate, and the exo-cyclic tin atom is hexa-coordinated geometry, while the complex 2 is seven-coordinated geometry. The nitrogen atom of the aromatic ring participates in the interactions with the Sn atom.  相似文献   

16.
The study of the reactivity of the cyclopalladated complex [Pd{[(η5-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}Cl] (1c) with the alkynes R1-CC-R1 (with R1 = CO2Me, Ph or Et) is reported.Compound 1c reacts with the equimolar amount of MeO2C-CC-CO2Me in refluxing CH2Cl2 to give [Pd{[(MeO2C-CC-CO2Me)(η5-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}Cl] (2c), which arises from the monoinsertion of the alkyne into the σ[Pd-C(sp2, ferrocene)] bond.However, when the reaction was performed using Ph-CC-Ph or Et-CC-Et no evidence of the insertion of these alkynes into the σ[Pd-C(sp2, ferrocene)] bond was detected.In contrast with these results, when 1c was treated with the Tl[BF4] followed by the removal of the TlCl formed and the subsequent addition of MeO2C-CC-CO2Me the reaction gave 2c and [Pd{[(MeO2C-CC-CO2Me)25-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}][BF4] (3c); but when the alkyne was R1-CC-R1 (with R1 = Ph or Et), the ionic palladacycles [Pd{[(R1-CC-R1)25-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}][BF4] · CH2Cl2 [with R1 = Ph (5c) or Et (6c)] were isolated. In compounds 3c, 5c and 6c, the mode of binding of the butadienyl unit is η3. The reactions of 2c, 3c, 5c and 6c with PPh3 are also reported. The results obtained from these studies reveal that the σ(Pd-S) bond in 2c is more prone to cleave than in 4c-6c. X-ray crystal structures of 2c, 5c and [Pd{[(MeO2C-CC-CO2Me)(η5-C5H3)-CHN-(C6H4-2-SMe)]Fe(η5-C5H5)}Cl(PPh3)] (7c), are also described. Compound 7c arises from 2c by cleavage of the Pd-S bond and the incorporation of a PPh3 in the coordination sphere of the palladium. A parallel study focused on the reactions of [Pd{[2-CH2-4,6-Me2-C6H2]-CHN-(C6H4-2-SMe)}Cl] (1d) (with a [Csp3,N,S] terdentate group) with the three alkynes reveals that the σPd-C(sp2, ferrocene)] bond of 1c is more reactive than the σ[Pd-C(sp3)] bond of 1d.  相似文献   

17.
Cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4Hg)3 readily reacts with N,N-dimethylacetamide and n-butyronitrile to form the complexes {[(o-C6F4Hg)3](MeCONMe2)2} and {[(o-C6F4Hg)3](PrnCN)}, respectively. According to X-ray diffraction data, the amide ligands are located above and below the plane of the macrocycle, each being coordinated to all Hg atoms of the macrocycle through the O atom. The nitrile ligand is bound to the macrocycle through the N atom, all Hg atoms being also involved in this bonding.  相似文献   

18.
In the hydrolysis reaction of dichlorosilanes having an intramolecular coordinating atom, dcisiloxane-1,3-diols, [(OH){o-(CH3)2NCH2-C6H4}RSi]2O(R=CH2CH (1), C6H5 (2), o-(CH3)2NCH2C6H4 (3), Me (4)), were obtained in high yields. The results of the crystal structure analyses of meso-2, rac-2a, rac-2b and 3 are reported. They showed strong intramolecular hydrogen bondings between the hydroxy group and the nitrogen atom. We have also found that the diastereomeric isomerization of meso-2 to rac-2 in CDCl3 solvent containing moisture occurred to result in the 55:45 equilibrium mixtures of the isomers and vice versa.  相似文献   

19.
A Mannich condensation of 2,4-di-tert-butylphenol, p-bromophenethylamine, and formaldehyde followed by a Sonogashira coupling of the resulting 3-(4-bromophenethyl)-6,8-di-tert-butyl-3,4-dihydro-2H-benz[1,3]oxazine (1-Br) with TMSCCH gave acetylenic benzoxazine 1-C2TMS which was a precursor for polyynic derivatives. Firstly, it was deprotected with K2CO3 in iPrOH/MeOH to give the terminal acetylene 1-C2H, which was subsequently dimerized to the symmetrical diyne 1-C4-1. Next, 1-C2H was transformed to 1-C4TMS via a Cadiot-Chodkiewicz coupling, and then 1-C4TMS was homocoupled with in situ deprotection to give octatetrayne 1-C8-1. X-ray diffraction studies of 1-C8-1 showed distinctive chain bending and a packing analysis revealed the potential for 1,n-topochemical polymerization that implies a cross-linking opportunity.  相似文献   

20.
Reactions between [Fe(η-C5H5)(MeCO)(CO)(L)], L = PPh3 (1), PMe3 (2), PPhMe2 (3), PCy3 (4), CO (5), and B(C6F5)3 give new complexes [Fe(η-C5H5){MeCOB(C6F5)3}(CO)(L)] L = PPh3 (7), PMe3 (8), PPhMe2 (9), PCy3 (10), CO (11), where B(C6F5)3 coordinates selectively to the O-acyl groups. Hydrolysis of 7 gives [Fe(η-C5H5){HOB(C6F5)3}(CO)(PPh3)] (6). The X-ray structures of 6, 8 and 11 have been determined. Calculations, using density functional theory, demonstrate that the charge transfer to the acyl group on Lewis acid coordination is more significant in the σ than the π system. Both effects lead to a lengthening of the acyl C-O bond thus π populations cannot be inferred from the distance changes.  相似文献   

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