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1.
Complexes cis,trans-Fe(CO)2(PMe3)2RR′ (R = CH3, R′ = Ph (2); R = CH3, R′ = CHCH2 (3); R = CHCH2, R′ = Ph (4); R = R′ = CHCH2 (5); R = R′ = CH3 (6)) were prepared by reaction of cis,trans-Fe(CO)2(PMe3)2RCl (1) with organolithium reagents LiR′. All complexes were characterized in solution by IR and 1H, 31P and, in a few cases, 13C NMR mono- and bi-dimensional spectroscopies. Complexes 5 and 6 were structurally characterized by X-ray diffractometric methods. In solution complexes 2, 3 and 4 undergo slowly coupling of the σ-hydrocarbyl substituents leading to Fe(CO)3(PMe3)2 and other decomposition products. Complex 6 was very stable in solution in the absence of nucleophiles and in the solid state. Complex 5 transformed through intramolecular coupling of the vinyl groups into Fe(CO)(PMe3)24-butadiene) (7), which was characterized in solution by IR and NMR spectroscopies.  相似文献   

2.
The dinuclear nickel(II) complex [Ni2L(Cl)]+ (1), where (L)2− represents a 24-membered binucleating hexamine-dithiophenolate ligand, reacts readily with primary and secondary amines RR′NH in the presence of CO2 (1 bar) to give dinuclear monoalkyl- and dialkylcarbamate complexes [Ni2L(O2CNRR′)]+ (R = H, R′ = CH2Ph (2), R = H, R′ = n-Bu (3), R = H, R′ = n-Oct (4), R = H, R′ = CH2CH2OH (5), R = R′ = Et (6), and R = R′ = CH2CH2OH (7)). Complexes 2-7 can also be prepared by the reaction of 1 with CO2(air)/amine. The carbamate complexes are hydrolyzed in methanolic solution to give the known alkylcarbonate complex [Ni2L(O2COMe)]+ (8). These conversions are less rapid than the transesterification reactions of 8, due to a less electron-demanding carboxyl C(carbamate) atom. All new complexes were either isolated as perchlorate or tetraphenylborate salts and fully characterized by elemental analysis, UV/Vis, and IR spectroscopy. The structures of 2[BPh4] and 7[BPh4] have also been determined by X-ray crystallography. They confirm the presence of μ1,3-bridging alkylcarbamate units in the products.  相似文献   

3.
The new diiron alkynyl methoxy carbene complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO){C(OMe)CCR′}(Cp)2]+ (R = 2,6-Me2C6H3 (Xyl), R′ = Tol, 3a; R = Xyl, R′ = Ph, 3b; R = Xyl, R′=Bun, 3c; R = Xyl, R′=SiMe3, 3d; R = Me, R′ = Tol, 3e; R = Me, R′ = Ph, 3f) are obtained in two steps by addition of R′CCLi (R′ = Tol, Ph, Bun, SiMe3) to the carbonyl aminocarbyne complexes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)2(Cp)2]+ (R = Xyl, 1a; Me, 1b), followed by methylation of the resulting alkynyl acyl compounds [Fe2{μ-CN(Me)(R)}(μ-CO)(CO){C(O)CCR′}(Cp)2] (R = Xyl, R′ = Tol, 2a; R = Xyl, R′ = Ph, 2b; R = Xyl, R′ = Bun, 2c; R = Xyl, R′ = SiMe3, 2d; R = Me, R′ = Tol, 2e; R = Me, R′ = Ph, 2f). Complexes 3 react with secondary amines (i.e., Me2NH, C5H10NH) to give the 4-amino-1-metalla-1,3-dienes [Fe2{μ-CN(Me)(R)}(μ-CO)(CO){C(OMe)CHC(R′)(NMe2)}(Cp)2]+ (R = Xyl, R′ = Tol, 4a; R = Xyl, R′ = Ph, 4b; R = Me, R′ = Ph, 4c) and [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(Tol)(NC5H10)}(Cp)2]+, 5. The addition occurs stereo-selectively affording only the E-configured products. Analogously, addition of primary amines R′NH2 (R′ = Ph, Et, Pri) affords the 4-(NH-amino)-1-metalla-1,3-diene complexes [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(R)(NHR′)}(Cp)2]+ (R = Ph, 6a; Et, 6b; Pri, 6c). In the case of 6a, only the E isomer is formed, whereas a mixture of the E and Z isomers is present in the case of 6b,c, with prevalence of the latter. Moreover, the two isomeric forms exist under dynamic equilibrium conditions, as shown by VT NMR studies. Complexes 6 are deprotonated by strong bases (e.g., NaH) resulting in the formation of the neutral vinyl imine complexes [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){C(OMe)CHC(NR)(Tol)}(Cp)2] (R = Ph, 7a; Et, 7b; Pri, 7c); the reaction can be reverted by addition of strong acids. X-ray crystal structures have been determined for 3a[CF3SO3] · Et2O, 4c[CF3SO3], 6a[BF4] · CH2Cl2, 6c[CF3SO3] · 0.5Et2O and 7a · CH2Cl2.  相似文献   

4.
A new series of mono- and diphenylsubstituted silatranes and boratranes N(CH2CH2O)2(CHR3CR1R2O)MZ (M = Si, Z = CH2Cl, CCPh, H, OMenth, R1, R2, R3 = H, Ph; M = B, Z = nothing, R1, R2, R3 = H, Ph) have been synthesized. Both transalkoxylation and stepwise modification of a preformed metallatrane skeleton were used. The chloromethyl derivatives N(CH2CH2O)2(CHRCHRO)SiCH2Cl (R = H, Ph) react with tert-BuOK under intramolecular cycle expansion to give 1-tert-butoxy-2-carba-3-oxahomosilatranes N(CH2CH2O)(CH2CH2OCH2)(CHRCHRO)SiOtBu (R = H, Ph). The treatment of boratranes N(CH2CH2O)2(CH2CR1R2O)B (R1,R2 = H, Ph) with triflic acid and trimethylsilyl triflate results in the products of electrophilic attack at the nitrogen atom. The molecular structures of four silatranes and one boratrane bearing phenyl groups in the atrane skeleton were determined by the X-ray structure analysis.  相似文献   

5.
New silver(I) acylpyrazolonate derivatives [Ag(Q)], [Ag(Q)(PR3)]2 and [Ag(Q)(PR3)2] (HQ = 1-R1-3-methyl-4-R2(CO)pyrazol-5-one, HQBn = R1 = C6H5, R2 = CH2C6H5; HQCHPh2 = R1 = C6H5, R2 = CH(C6H5)2; HQnPe = R1 = C6H5, R2 = CH2C(CH3)3; HQtBu = R1 = C6H5, R2 = C(CH3)3; HQfMe = R1 = C6H4-p-CF3, R2 = CF3; HQfEt = R1 = C6H5, R2 = CF2CF3; R = Ph or iBu) have been synthesized and characterized in the solid state and solution. The crystal structure of 1-(4-trifluoromethylphenyl)-3-methyl-5-pyrazolone, the precursor of proligand HQfMe and of derivatives [Ag(QnPe)(PPh3)2] and [Ag(QnPe)(PiBu3)]2 have been investigated. [Ag(QnPe)(PPh3)2] is a mononuclear compound with a silver atom in a tetrahedrally distorted AgO2P2 environment, whereas [Ag(QnPe)(PiBu3)]2 is a dinuclear compound with two O2N-exotridentate bridging acylpyrazolonate ligands connecting both silver atoms, their coordination environment being completed by a phosphine ligand.  相似文献   

6.
Single crystal X-ray structural characterizations are recorded for an array of adducts of the form AgX:dppf (1:1)(n), X = simple (pseudo-)halide or oxy-anion, ‘dppf’ = bis(diphenyl phosphino)ferrocene, for adducts X = Cl (new phase), Br, I, SCN, OCN, CN, NO3 (new phase), O2CCH3, n = 2, the form being dimeric [(dppf-P,P′)Ag(μ-X)2Ag(P,P′-dppf)], for X = I, SCN, [Ag(μ-X)2(P-dppf-P′)2Ag′]; for X = O2CCF3, n = ∞, the form is an extended polymer: ?Ag(O · CO · CF3)(P-dppf-P′)Ag′(O?. A dichloromethane solvate phase of CuI:dppf (1:1)2 (also centrosymmetric) is also recorded. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (1H, 13C, 31P NMR, ESI MS) and in the solid state (IR). The topology of the structures in the solid state was found to depend on the nature of the counterion.  相似文献   

7.
Reaction of the lithium salts of N,N′-dialkyl-2-amino-4-imino-pent-2-enes, nacnacRLi(THF) (R = CH2Ph, Cy, nPr, iBu or S-CH(Me)Ph), with half an equivalent of CrCl2(THF)x yielded the homoleptic complexes (nacnacR)2Cr. All complexes were characterized by X-ray diffraction studies and displayed a highly symmetric, square-planar coordination around the chromium center with strong boat-like distortions of the diketiminate ligands. Reaction of nacnacRLi(THF) (R = CH2Ph, Cy) with one equivalent of CrCl2(THF)x afforded the dimeric complexes {nacnacRCr(μ-Cl)}2.  相似文献   

8.
A series of organotin(IV) complexes with Schiff base ligand pyruvic acid 3-hydroxy-2-naphthoyl hydrazone [R2SnLY]2, L = 3-HO-C10H6-2-CONHNC(CH3)COOH, R = n-C4H9, Y = CH3OH (1), R = n-C4H9, Y = N (2), R = PhCH2 (3), R = Ph, Y = CH3OH (4), R = Me, (5) and [R3SnLY], L = 3-HO-C10H6-2-CONHNC(CH3)COOH, R = n-C4H9, Y = H2O, (6), R = Ph (7), R = Me (8) have been synthesized. These complexes have been characterized by elemental analysis, IR, 1H and 119Sn NMR spectra. The crystal and molecular structure of complexes 1, 2 and 6 have been determined by X-ray single crystal diffraction. Results showed that complex 1 has a dimeric structure and the central tin atom is rendered seven-coordinate in a distorted pentagonal-bipyramid configuration. The complex 2 has a monoclinic structure and the central tin atom is rendered six-coordinate in octahedrally configuration with a planar of SnO3N unit and two apical aryl C atoms. And the whole structure consists of molecular units connected by weak intermolecular Sn?N and O-H?N interactions. In the complex 6, the central tin atom is five-coordinate in distorted trigonal-bipyramidal geometry.  相似文献   

9.
Single crystal X-ray structural characterizations are recorded for a number of adducts of MX:dpex (2:3) stoichiometry (MX = simple univalent copper or silver salt; dpex = Ph2E(CH2)xEPh2 (E = P, As)). CuX:dppe (2:3) (X = Cl, Br, I, CN) are binuclear [(dppe-P,P′)CuX(P-dppe-P′)CuX(P,P′-dppe)], all centrosymmetric. AgX:dpex (2:3) (dpex = ‘dpae’ (Ph2As(CH2)2AsPh2), X = Br, F3CCO2 (= ‘tfa’), F3CSO3 (≡ ‘tfs’); dpex = ‘dpape’ (Ph2As(CH2)2PPh2), X = CN, SCN, OClO3) are one-dimensional polymers ?-E′)1AgX(E-dpex-E′)2-AgX(E-dpex-E′)1AgX?, P, As sites scrambled in the latter. AgNO3:dpam (2:3) is also a one-dimensional polymer, ?AgO·NO·OAg(As-dpam-As)AgO·NO·OAg? (‘dpam’ ≡ Ph2As(CH2)2AsPh2). AgX:dpae (2:3) (X = I, CN, ClO4, NO3) and AgX:dpape (2:3) (X = Br, I, NO3) are two-dimensional polymers with large 30-membered macrocyclic rings; similar webs are found for dppx ligands in AgOH:dppb (2:3) and AgNCO, Agtfa:dpph (2:3) with 42- and 54-membered rings. Complexes AgX:dpape (1:3) (X = Cl, Br) are defined as mono-nuclear [XAg(Ph2P(CH2)2AsPh2)3] arrays, the unidentate ligands predominantly P-bound. Synthetic procedures for the adducts are reported, selected compounds being characterized both in solution (1H, 31P NMR, ESI MS) and in the solid state (IR).  相似文献   

10.
11.
Twenty-one adducts of the form AgX:ER3:L (1:1:1) (X = CF3COO (‘tfa’), CH3COO (‘ac’), E = P, As; R = Ph, cy, o-tolyl; L = 2,2′-bipyridyl (‘bpy’)-based ligand) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, 1H, 19F and 31P NMR) and single crystal X-ray diffraction studies. The resulting complexes are predominantly of the form [(R3E)AgL]+X, with a trigonal EAgN2 coordination environment, the planarity of which may be perturbed by the approach of anion or solvent. The carboxylate anions have been found to be uni-, or semi-bidentate, or also completely ionic, as in the complexes [Ag(PPh3)(bpy)(H2O)](tfa) and [Ag(PPh3)(dpk · H2O)](tfa) (‘dpk · H2O’ = bis(2-pyridyl)ketone (hydrated)). The complexes Agac:PPh3:dpa (1:1:1) and Agac:P(o-tol)3:dpa:MeCN (1:1:1:1) are dinuclear, with bridging unidentate acetate and terminal unidentate dpa (‘dpa’ = bis(2-pyridyl)amine).  相似文献   

12.
Consecutive synthesis methodologies for the preparation of a series of copper(I) formates [LmCuO2CH] (L = nBu3P: 4a, m = 1; 4b, m = 2; 5, L = [Ti](CCSiMe3)2, m = 1, [Ti] = (η5-C5H4SiMe3)2Ti) and [LmCuO2CH·HO2CR] (L = nBu3P: 7a, m = 1, R = H; 7b, m = 2, R = H; 7c, m = 2, R = Me; 7d, m = 2, R = CF3; 7e, m = 2, R = Ph. L = (cC6H11)3P, R = H: 8a, m = 2; 8b, m = 3. L = (CF3CH2O)3P, R = H: 9a, m = 2; 9b, m = 3. L = (CH3CH2O)3P, R = H: 10a, m = 2; 10b, m = 3. L = [Ti](CCSiMe3)2; m = 1: 11a, R = H; 11b, R = Ph) is reported using [CuO2CH] (1) and L (2a, L = nBu3P; 2b, L (cC6H11)3P; 2c, L = (CF3CH2O)3P; 2d, L = (CH3CH2O)3P; 3, L = [Ti](CCSiMe3)2) as key starting materials. Addition of formic acid (6a) or carboxylic acid HO2CR (6b, R = Me; 6c, R = CF3; 6d, R = Ph) to the afore itemized copper(I) formates 4 and 5 gave metal-organic or organometallic 7-11. The molecular structures of 8a and 11a in the solid state are reported showing a threefold coordinated copper(I) ion, setup by either two coordinatively-bonded phosphorus atoms and one formate oxygen atom (8a) or two π-bonded alkyne ligands and one oxygen atom (11a). A formic acid molecule is additionally hydrogen-bonded to the CuO2CH moiety. The use of 7b as suitable precursor for the deposition of copper onto TiN-coated oxidized silicon wafers by the spin-coating process below 300 °C is described. Complex 7b offers an appropriate transformation behavior into metal phase by an elimination-decarboxylation mechanism. The morphology of the copper films strongly depends on the annealing conditions. A closed grain network densified by a post-treatment is obtained (8 °C min−1, N2/H2 carrier gas). Hydrogen post-anneal to 420 °C after film deposition gave a copper film showing resistivities from 2.5 to 3.7 μΩ cm. This precursor was also used for gap-filling processes.  相似文献   

13.
《Inorganica chimica acta》2006,359(7):2309-2313
Deprotonated 3-(2-fluorophenyl)-1-(4-acetylphenyl)triazene reacts with Hg(CH3COO)2 in tetrahydrofuran to give light yellow crystals of [HgII(RPhNNNPhR′)2]n (R = acetyl, R′ = F). The new polymeric triazenide complex of Hg(II) belongs to the monoclinic space group C2/c. The lattice of [HgII(RPhNNNPhR′)2]n can be viewed as a bidimensional assembly of planar tectons [HgII(RPhNNNPhR′)2], occurring through metallocene alike Hg(II)-η22-arene π-interactions along the crystallographic axis b and non classical C-H?O bonding along the axis a.  相似文献   

14.
Single crystal X-ray studies have defined the structures of a number of adducts of the form MX:dpex (2:1), M = univalent coinage metal (Cu, Ag), X = (pseudo-)halide, dpex = bis(diphenylpnicogeno)alkane, Ph2E(CH2)xEPh2, E = P, As, of diverse types, some novel. The adducts of AgCl,Br:dppm and AgNCO:dpem (x = 1) are tetranuclear as is the AgNO3:dppp (x = 3) array, all derivative of the familiar ‘step’ structure while the combination CuCN:dppm yields a two-dimensional web of twenty-membered macro/metallacycles. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (1H, 13C, 31P NMR, ESI MS) and in the solid state (IR).  相似文献   

15.
Reaction of the mercury(II) amide Hg[N(SiMe3)3]2 with 3,3′-disubstituted binaphthols (HO)2C20H10(R)2-3,3′ (R = SiMe3, SiMe2Ph, SiMePh2, SiPh3) in a 2:1 stoichiometric ratio furnishes four hexacyclic 1,7-disilylsubstituted derivatives of peri-xanthenoxanthene (PXX). Reaction of these two reagents in a 1:1 ratio results in a mixture of the hexacyclic products as well as the related pentacyclic species which contain one hydroxyl group and only one C-O-C ring fusion. The structures of three of the hexacyclic products (R = SiMe3, SiMe2Ph, SiMePh2) and one of the pentacyclic products (R = SiMe3) have been obtained. The reaction of Hg[N(SiMe3)3]2 with the 3,3′-disubstituted binaphthols proceeds via an intramolecular electrophilic aromatic substitution reaction and several intermediates in this process have been detected using NMR (1H and 199Hg) spectroscopy.  相似文献   

16.
Ten novel adducts of the form AgClO4:PR3:L (1:1:1) (R = Ph, cy, o-tolyl; L = 2,2′-bipyridyl (‘bpy’), 2,2′-biquinoline (‘bq’), bis(2-pyridyl)amine (‘dpa’), bis(2-picolyl)amine (‘dpca’)) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, 1H and 31P NMR) and single crystal X-ray diffraction studies. The solid state molecular structures show that the complexes predominantly take the form [(R3P)AgL]+X, with a trigonal PAgN2 coordination environment, where the approach of the anion or the solvent may perturb the planarity of the silver environment. The ClO4 anion shows uni- or semi-bidentate coordination, except in the complexes AgClO4:PR3:dpca (1:1:1) (R = Ph and o-tolyl), where the anion remains uncoordinated and the dpca donor is a three-coordinate pincer-like ligand.  相似文献   

17.
A metathesis reaction of [CpMCl2(PR3)] [M = Rh, R = Ph (1), Me (3); M = Ir, R = Ph (2), Me (4)] takes place in the presence of potassium butadienesulfinate (SO2CHCHCHCH2)K (9) to afford the mononuclear compounds [CpM(Cl)(PR3)(η1-SO2CHCHCHCH2)] [M = Rh, R = Ph (11S), (11W); M = Rh, R = Me (13S), (13W)] and [M = Ir, R = Ph (12S); M = Ir, R = Me (14S), (14W)] under different reaction conditions. The addition of PR3 (R = Ph, Me) to CpIr(Cl)[(1,2,5-η)-SO2CHCHCHCH2] (7) affords the corresponding iridium isomers 12S, 12W and 14S, in a non-selective reaction, along with the corresponding dichloride compounds 2 or 4. The 1H and 13C{1H} NMR data are consistent with the butadienesulfonyl ligands coordinated exclusively through the sulfur atom, and they show the presence of two isomers, described as the S and W conformers, which can be isolated separately. There is clear evidence that these isomers correspond to the kinetic and thermodynamic derivatives, respectively.  相似文献   

18.
New silver(I) derivatives [Ag{HnB(btz)4 − n}(PR3)x] (n = 1 or 2, x ranging from 1 to 3), containing monodentate tertiary phosphines and anionic poly(benzotriazol-1-yl)borates, have been prepared from the reaction of AgNO3 with PR3 (R = Ph, o-tolyl, m-tolyl, p-tolyl, Bns) and K[H2B(btz)2], or K[HB(btz)3] (Hbtz = 1,2,3-benzotriazole). When the reaction between K[H2B(btz)2] and AgNO3 was carried out in the presence of dppe (1,2-bis(diphenylphosphino)ethane), or dppf (1,1′-bis(diphenylphosphino)ferrocene), compounds [Ag{H2B(btz)2}]2(L) (L = dppe or dppf) formed, the diphosphine acting as a bidentate bridging P2-donor. Solid state and solution properties of all complexes have been investigated through analytical and spectroscopic measurements (IR, 1H, 31P NMR), the 1H and 31P NMR spectra being interpreted in terms of equilibria that involve mono- and di-nuclear complexes. Adducts [Ag{HB(btz)3}(PPh3)3] · (1/2H2O) and [Ag{H2B(btz)2}]2 (dppf) have been characterised by single crystal X-ray studies. In the former, the HB(btz)3 is unidentate in an NAgP3 coordination environment; the latter is a dimer, the dppf bridging the two silver atoms, while the H2B(btz)2 ligand, which chelates one silver, bridges to the second also, the array having 2-symmetry.  相似文献   

19.
Syntheses and spectroscopic features (IR, NMR and ESI MS) are reported for five 1:2 adducts of CuX with dppe (X = I, ClO4, NCS, O3SCF3 (tfs) BH4; dppe = Ph2P(CH2)2PPh2). ESI MS and 31P NMR spectroscopy indicate that these species dissociate in solution yielding free diphosphine and 3:2 species. A single crystal X-ray structure determination has been carried out on Cu(dppe)2NCS defining a four-coordinate complex of the form [(P,P′-dpex)M(P-dpex)X] for M = Cu, the thiocyanate being N-bound; the ionic [Cu(P,P′-dppe)2]tfs has also been structurally characterized.  相似文献   

20.
Coordination compounds of general formula MX42-O(R)CH2CH(R′)OR′′], 2a-i, have been prepared in high yield upon addition of a variety of 1,2-dialkoxyalkanes, ROCH2CH(R′)OR′′, to MX4 (M = Ti, X = F, 1a, I, 1b; M = Zr, X = Br, 1c, I, 1d). The new complexes have been characterized by elemental analysis and NMR spectroscopy. The thermal stability of 2 has been studied. Fragmentation of the TiI4 adducts takes place in chloroform solution at 90 °C: after hydrolysis of the reaction mixtures, MeI and CH2ICH2I have been detected from TiI4[dme] [dme = MeO(CH2)2OMe], MeI and Me2O from TiI4[MeOCH2CH(Me)OMe], and MeI, CH2ICH2I, Me2O, CH2ClI from TiI4[MeO(CH2)2OCH2Cl]. The diether MeO(CH2)2OCH2Cl is thermally activated also when coordinated to ZrX4 (X = Br, I): after hydrolysis, MeBr, CH2BrCH2Br, O(CH2CH2Cl)2 and Me2O (X = Br) and MeI, CH2ClI and CH2ICH2I (X = I) have been found, respectively.  相似文献   

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