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1.
The phosphinoalkenes Ph2P(CH2)nCH=CH2 (n= 1, 2, 3) and phosphinoalkynes Ph2P(CH2)n C≡CR (R = H, N = 2, 3; R = CH3, N = 1) have been prepared and reacted with the dirhodium complex (η−C5H5)2Rh2(μ−CO) (μ−η2−CF3C2CF3). Six new complexes of the type (ν−C5H5)2(Rh2(CO) (μ−η1:η1−CF3C2CF3)L, where L is a P-coordinated phosphinoalkene, or phosphinoalkyne have been isolated and fully characterized; the carbonyl and phosphine ligands are predominantly trans on the Rh---Rh bond, but there is spectroscopic evidence that a small amount of the cis-isomer is formed also. Treatment of the dirhodium-phosphinoalkene complexes with (η−CH3C5H4)Mn(CO)2thf resulted in coordination of the manganese to the alkene function. The Rh2---Mn complex [(η−C5H5)2Rh2(CO) (μ−η1:η1−CF3C2CF3) {Ph2P(CH2)3CH=CH2} (η−CH3C5H4)Mn(CO)2] was fully characterized. Simi treatment of the dirhodium-phosphinoalkyne complexes with Co2(CO)8 resulted in the coordination of Co2(CO)6 to the alkyne function. The Rh2---Co2 complex [(η−C5H5)2Rh2(CO) (μ−η1:η1−CF3C2CF3) {Ph2PCH2C≡CCH3}Co2(CO)2], C37H25Co2F6O7PRh2, was fully characteriz spectroscopically, and the molecular structure of this complex was determined by a single crystal X-ray diffraction study. It is triclinic, space group (Ci1, No. 2) with a = 18.454(6), B = 11.418(3), C = 10.124(3) Å, = 112.16(2), β = 102.34(3), γ = 91.62(3)°, Z = 2. Conventional R on |F| was 0.052 fo observed (I > 3σ(I)) reflections. The Rh2 and Co2 parts of the molecule are distinct, the carbonyl and phosphine are mutually trans on the Rh---Rh bond, and the orientations of the alkynes are parallel for Rh2 and perpendicular for Co2. Attempts to induce Rh2Co2 cluster formation were unsuccessful.  相似文献   

2.
A series of cationic nickel complexes [(η3-methally)Ni(PP(O))]SbF6 (1–4) [PP(O) = Ph2P(CH2)P(O)Ph2 (dppmO) (1), Ph2P(CH2)2P(O)Ph2 (dppeO) (2), Ph2P(CH2)3P(O)Ph2 (dpppO) (3), pTol2P(CH2)P(O)pTol2 (dtolpmO) (4)] has been synthesized in good yields by treatment of [(η3-methally)NiBr]2 with biphosphine monoxides and AgSbF6. The ligands are coordinated in a bidentate way. Starting from [(η3-all)PdI]2 the cationic complexes [(η3-all)PP(O))]Y (8–14). [PP(O) = dppmO, dppeO, dpppO, dtolpmO;Y = BF4, SbF6, CF3SO3, pTolSO3] were synthesized in good yields. The coordination mode of the ligand is dependent on the backbone and the anion, revealing a monodentate coordination with dppmO for stronger coordinating anions. The intermediates [(η3-all)Pd(I)(PP(O)-κ1-P)] (5–7) [PP(O) = dppmO (5), dppeO (6), dtolpmO (7)] were isolated and characterized. Neutral methyl complexes [(Cl)(Me)Pd(PP(O))] (15–18). [PP(O) = dppmO (15), dppeO (16), dpppO (17), dtolpmO (18)] can easily be obtained in high yields starting from [(cod)PdCl2]. For dppmO two different routes are presented. The structure of [(Me)(Cl)Pd{;Ph2P(CH2-P(O)Ph2-κ2-P,O};] · CH2Cl2 (15) with the chlorine atom trans to phosphorus was determined by X-ray diffraction.  相似文献   

3.
The new tripodal phosphine CH3C{CH2P(m-CF3C6H4)2}3, CF3PPP, was prepared by reacting CH3C(CH2Br)3 with Li+P(m-CF3C6H4)2−, the latter being best obtained by adding Li+NiPr2− to PH(m-CF3C6H4)2. The rhodium complexes [RhCl(CO)(CF3PPP)], [Rh(LL)(CF3PPP)](CF3SO3) (LL = 2 CO or NBD), [RhX3(CF3PPP)], [RhX(MeCN)3(CF3PPP)](CF3SO3)2 (X = H and Cl), [RhCl2(MeCN)(CF3PPP)](CF3SO3) and [Rh(MeCN)3(CF3PPP)](CF3SO3)3 were prepared and characterized. The X-ray crystal structure of [Rh(NBD)(CF3PPP)](CF3SO3) is reported. The lower oxygen sensitivity of the CF3PPP rhodium(I) complexes, relative to the corresponding species with the parent ligand CH3C(CH2PPh2)3, is attributed to the higher effective nuclear charge on the metal centers caused by the presence of the six CF3 substituents on the terdentate phosphine. A similar effect may be responsible for the easier hydrolysis of the CF3PPP-containing, cationic rhodium(III) complexes relative to the corresponding compounds of the parent ligand.  相似文献   

4.
The reaction of TiCl4 with Li2[(SiMe2)2(η5-C5H3)2] in toluene at room temperature afforded a mixture of cis- and trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] in a molar ratio of 1/2 after recrystallization. The complex trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] was hydrolyzed immediately by the addition of water to THF solutions to give trans-[(TiCl2)2(μ-O){(SiMe2)2(η5-C5H3)2}] as a solid insoluble in all organic solvents, whereas hydrolysis of cis-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] under different conditions led to the dinuclear μ-oxo complex cis-[(TiCl2)2)(μ-O){(SiMe2)2(η5-C5H3)2}] and two oxo complexes of the same stoichiometry [(TiCl)2(μ-O){(SiMe2)2(η5-C5H3)2}]2(μ-O)2 as crystalline solids. Alkylation of cis- and trans-[(TiCl3)2{(SiMe2)2(η5-C5H3)2}] with MgCIMe led respectively to the partially alkylated cis-[(TiMe2Cl)2{(SiMe2)2(η5-C5H3)2}] and the totally alkylated trans-[(TiMe3)2{(SiMe2)2(η5-C5H3)2}] compounds. The crystal and molecular structure of the tetranuclear oxo complex [(TiCl)2(μ-O){(SiMe2)2(η5-C5H3)2}]2(μ-O)2 was determined by X-ray diffraction.  相似文献   

5.
Reaction of RuCl(η5-C5H5(pTol-DAB) with AgOTf (OTf = CF3SO3) in CH2Cl2 or THF and subsequent addition of L′ (L′ = ethene (a), dimethyl fumarate (b), fumaronitrile (c) or CO (d) led to the ionic complexes [Ru(η5-C5H5)(pTol-DAB)(L′)][OTf] 2a, 2b and 2d and [Ru(η5-C5H5)(pTol-DAB)(fumarontrile-N)][OTf] 5c. With the use of resonance Raman spectroscopy, the intense absorption bands of the complexes have been assigned to MLCT transitions to the iPr-DAB ligand. The X-ray structure determination of [Ru(η5-C5H5)(pTol-DAB)(η2-ethene)][CF3SO3] (2a) has been carried out. Crystal data for 2a: monoclinic, space group P21/n with A = 10.840(1), b = 16.639(1), C = 14.463(2) Å, β = 109.6(1)°, V = 2465.6(5) Å3, Z = 4. Complex 2a has a piano stool structure, with the Cp ring η5-bonded, the pTol-DAB ligand σN, σN′ bonded (Ru-N distances 2.052(4) and 2.055(4) Å), and the ethene η2-bonded to the ruthenium center (Ru-C distances 2.217(9) and 2.206(8) Å). The C = C bond of the ethene is almost coplanar with the plane of the Cp ring, and the angle between the plane of the Cp ring and the double of the ethene is 1.8(0.2)°. The reaction of [RuCl(η5-C5H5)(PPh)3 with AgOTf and ligands L′ = a and d led to [Ru(η5-C5H5)(PPh3)2(L′)]OTf] (3a) and (3d), respectively. By variable temperature NMR spectroscopy the rottional barrier of ethene (a), dimethyl fumarate (b and fumaronitrile (c) in complexes [Ru(η5-C5H5)(L2)(η2-alkene][OTf] with L2 = iPr-DAB (a, 1b, 1c), pTol-DAB (2a, 2b) and L = PPh3 (3a) was determined. For 1a, 1b and 2b the barrier is 41.5±0.5, 62±1 and 59±1 kJ mol−1, respectively. The intermediate exchange could not be reached for 1c, and the ΔG# was estimated to be at least 61 kJ mol−. For 2a and 3a the slow exchange could not be reached. The rotational barrier for 2a was estimated to be 40 kJ mol−. The rotational barier for methyl propiolate (HC≡CC(O)OCH3) (k) in complex [Ru(η5-C5H5)(iPr-DAB) η2-HC≡CC(O)OCH3)][OTf] (1k) is 45.3±0.2 kJ mol−1. The collected data show that the barrier of rotational of the alkene in complexes 1a, 2a, 1b, 2b and 1c does not correlate with the strength of the metal-alkene interaction in the ground state.  相似文献   

6.
The hydrothermal reactions of (Ph4P)[VO2Cl2] and H2C2O4 at 150 and 125°C yield (Ph4P)2[V2O2(H2O)2(C2O4)3]·4H2O (1) and (Ph4P)[VOCl(C2O4)] (2), respectively. The structure of the molecular anion of 1 consists of a binuclear unit of oxovanadium(IV) octahedra bridged by a bisbidentate oxalate group. The VO6 coordination geometry at each vanadium site is defined by a terminal oxo group, an aquo ligand, and four oxygen donors — two from the bisbidentate bridging oxalate and two from the terminal bidentate oxalate. The structure of 2 consists of discrete Ph4P+ cations occupying regions between [VOCl(C2O4)]−∞ spiral chains. The structure of the one-dimensional anionic chain exhibits V(IV) octahedra bridged by bisbidentate oxalate groups. Crystal data: 1·4H2O, monoclinic P21/n, A = 12.694(3), B = 12.531(3), C = 17.17(3) Å, β = 106.32(2)°, V = 2621.3(13) Å3, Z = 2, Dcalc = 1.501 g cm−3, structure solution and refinement converged at a conventional residual of 0.0518; 2, tetragonal P43, A = 12.145(2), C = 15.991(3) Å, V = 2358.7(12) Å3, Z = 4, R = 0.0452.  相似文献   

7.
It is shown that the reaction of RhCl3·3H2O with acetonitrile normally produces mixtures of mer- and fac-[RhCl3(CH3CN)3] (1a and 1b, respectively). The IR and 1H NMR spectra of these isomers were re-investigated. Their two-dimensional (103Rh,1H) NMR spectra were also recorded. Equilibrium and exchange studies of 1a and 1b in CD3C were performed. It was found that in 1a the exchange rate of the nitrile molecule trans to Cl is much faster than those of mutually trans nitriles. Also the nitrile molecules in 1b underwent fast exchange in CD3CN; however, their rate was slightly faster than that of the more labile CH3CN in 1a. The X-ray crystal structure of mer-[RhCl3(CH3CN)3]·CH3CN (1c) was determined. Crystal data: triclinic space group

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.  相似文献   

8.
The chloro complexes trans-[Pt(Me)(Cl)(PPh3)2], after treatment with AgBF4, react with 1-alkynes HC---C---R in the presence of NEt3 to afford the corresponding acetylide derivatives trans-[Pt(Me) (C---C---R) (PPh3)2] (R = p-tolyl (1), Ph (2), C(CH3)3 (3)). These complexes, with the exception of the t-butylacetylide complex, react with the chloroalcohols HO(CH2)nCl (n = 2, 3) in the presence of 1 equiv. of HBF4 to afford the alkyl(chloroalkoxy)carbene complexes trans-[Pt(Me) {C[O(CH2)nCl](CH2R) } (PPh3)2][BF4] (R = p-tolyl, N = 2 (4), N = 3 (5); R=Ph, N = 2 (6)). A similar reaction of the bis(acetylide) complex trans-[Pt(C---C---Ph)2(PMe2Ph)2] with 2 equiv. HBF4 and 3-chloro-1-propanol affords trans-[Pt(C---CPh) {C(OCH2CH2CH2Cl)(CH2Ph) } (PMe2Ph)2][BF4] (7). T alkyl(chloroalkoxy)-carbene complex trans-[Pt(Me) {C(OCH2CH2Cl)(CH2Ph) } (PPh3)2][BF4] (8) is formed by reaction of trans-[Pt(Me)(Cl)(PPh3)2], after treatment with AgBF4 in HOCH2CH2Cl, with phenylacetylene in the presence of 1 equiv. of n-BuLi. The reaction of the dimer [Pt(Cl)(μ-Cl)(PMe2Ph)]2 with p-tolylacetylene and 3-chloro-1-propanol yields cis-[PtCl2{C(OCH2CH2CH2Cl)(CH2C6H4-p-Me}(PMe2Ph)] (9). The X-ray molecular structure of (8) has been determined. It crystallizes in the orthorhombic system, space group Pna21, with a = 11.785(2), B = 29.418(4), C = 15.409(3) Å, V = 4889(1) Å3 and Z = 4. The carbene ligand is perpendicular to the Pt(II) coordination plane; the PtC(carbene) bond distance is 2.01(1) Å and the short C(carbene)-O bond distance of 1.30(1) Å suggests extensive electronic delocalization within the Pt---C(carbene)---O moietry.  相似文献   

9.
From a mixture of cis- and trans-Ru(SH)2(dppm)2 (4), formed from reaction of H2S with trans-Ru(H)Cl(dppm)2 (2), a crystal of cis-4 has been isolated and its structure determined by X-ray analysis. The mercapto protons are located within the centrosymmetric structure, although the S-atoms are partially disordered (S–H1.06 Å). The thiolate complexes, trans-Ru(H)SR(dppm)2 (R=Ph, 5a; C6F5, 5b), have been isolated from reaction of trans-2 with 1 equiv. of RSH. trans-Ru(H)SH(dppm)2 (3) has been isolated from reaction of H2S with a mixture of cis- and trans-Ru(H)2(dppm)2 (1). An improved synthetic route for 1 is presented.  相似文献   

10.
HRu2Fe2PdC(CO)12 (η3-ß-C10H15) cluster was prepared in the reaction of (Et4N) [HFe2Ru2C(CO)12] with [Pd(η3-ß-C10H15)Cl]2. X-ray structural study of HRu2Fe2PdC(CO)12 (η3-ß-C10H15) (where ß-C10H15 is ß-pinenyl) revealed a wing-tip butterfly geometry of the metal core and (1R, 2S, 3S, 5R) absolute configuration for both crystallography independent molecules in the crystal. Chiroptical properties of this cluster are compared with other clusters containing a Pd(η3-ß-C10H15) fragment and discussed.  相似文献   

11.
Reaction of tetrathiafulvalene carboxylic acid (TTFCO2H) with paddlewheel dirhodium complex Rh2(ButCO2)4 yielded TTFCO2-bridged complexes Rh2(ButCO2)3(TTFCO2) (1) and cis- and trans-Rh2(ButCO2)2(TTFCO2)2 (cis- and trans-2). Their triethylamine adducts [1(NEt3)2] and cis-[2(NEt3)2] were purified and isolated with chromatographic separation, and characterized with single crystal X-ray analysis. Trans-[2(NEt3)2] is not completely separated from a mixture of cis- and trans-[2(NEt3)2], but its single crystals were obtained from a solution of the mixture. A three-step quasi-reversible oxidation process was observed for 1 in MeCN. The first two steps correspond to the oxidation of the TTFCO2 moiety and the last one is the oxidation of the Rh2 core. The oxidation of cis-2 is observed as a two-step process with very similar E1/2 values to those of the first two processes for 1. Both 1+ and cis-22+ in MeCN at room temperature show isotropic ESR spectra with a g value of 2.008 and aH = 0.135 mT for two equivalent H atoms and aH = 0.068 mT for one H atom. The redox and ESR data of cis-2 suggest that the intramolecular interaction between the TTF moieties is very small.  相似文献   

12.
The reaction of RuCl3(H2O), with C5Me4CF3J in refluxing EtOH gives [Ru2(η5-C5Me1CF2)2 (μ-Cl2] (20 in 44% yield. Dimer 2 antiferromagnetic (−2J=200 cm1). The crystal structures of 2 (rhombohedral system, R3 space group, Z=9, R=0.0589) and [Rh2(η5-C5Me4CF3(2Cl2(μ-Cl)2] (3) (rhombohedral system. space group, Z = 9, R = 0.0641) were solved; both complexes have dimeric structures with a trans arrangement of the η5-C5Me4CF4 rings. Comparison of the geometry of 2 and 3 with those of the corresponding η5-C5Me5 complexes shows that lowering the ring symmetry causes significant distortion of the M2(μ-Cl)2 moiety. The analysis of the MCl3 fragment conformations in 2 and 3 and in the η5-C5ME5 analogues shows that they are correlated with the M---M distances. The Cl atoms are displaced by Br on reaction of 2 with KBr in MeOH to give the diamagnetic dimer [Ru2(η5-C5Me4CF3)2Br2 (μ-Br2] (4). Complex 2 reacts with O2 in CH2Cl2 solution at ambient temperature to form a mixture of isomeric η6-fulvene dimers [Ru2(η6-C5Me3CF3 = CH2)2Cl2(μ-Cl)2] (5). Reactions of 5 with CO and allyl chloride give Ru(η5-C5Me3CF3CH2Cl)(CO)2Cl (6) and Ru(η5-C5Me3CF3CF3CH2Cl)(η3-C3H5)Cl2 (7) respectively.  相似文献   

13.
The preparation and structural characterization of {Ru3(CO)11}2(1,4-bis(diphenylphosphino)benzene), a modified synthesis of 1,4-bis(diphenylphosphino)benzene, and the structural characterization of {Ru3(CO)11}2(bis(diphenylphosphino)ethane) are reported. In both compounds two metal cluster units are connected through ditertiary-phosphine ligands. Both molecules consist of centrosymmetric units in which the diphosphine ligands are largely covered by the triangular ruthenium clusters. No direct interaction between the two cluster units occurs within individual molecules. Molecular packing in the solid state is dominated by interactions between sets of carbon monoxide ligands in motifs that were previously identified in the solid state structure of the parent cluster, Ru3(CO)12.  相似文献   

14.
An improved synthetic procedure for pentabenzylcyclopentadiene Bz5C5H was developed. Six new organomolybdenum and organotungsten halides η5-Bz5C5M(CO)3X(M = Mo, W; X = Cl, Br, I) were syntesized through the reaction of η5-Bz5C5M(CO)3Li (derived from Bz5C5H, n-BuLi and M(CO)6) with PCl3, PBr3 or I2 and characterized by elemental analysis, IR and 1H NMR spectroscopy. The structure of η5-Bz5C5Mo(CO)3I was determined by single-crystal X-ray diffraction techniques. It crystallized in the monoclinic space groupp P2/c with cell parameters a = 13.294(4), B = 15.147(4), C = 19.027(3) Å, β = 108.32(2)°, V = 3637(2) Å3, Z = 4 and Dx = 1.50 g cm−3. The final R value was 0.035 for 4564 observed reflections.  相似文献   

15.
New mixed metal complexes SrCu2(O2CR)3(bdmap)3 (R = CF3 (1a), CH3 (1b)) and a new dinuclear bismuth complex Bi2(O2CCH3)4(bdmap)2(H2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi2O3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm−1. Crystal data for 1a: C27H51N6O9F9Cu2Sr/THF, monoclinic space group P21/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å3, Z = 2; for 1b: C27H60N6O9Cu2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å3, Z = 8; for 2: C22H48O11N4Bi2, monoclinic space group P21/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å3, Z = 4.  相似文献   

16.
The reaction between the redox-active diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) and the dirhenium compound Re2(CO)8(μ-H)(μ-η1,η2-C CPh) in CH2Cl2 at room temperature proceeds by CO loss to give the dirhenium complex Re2(CO)7(bpcd)(μ-H)(η1-C CPh) (1). This new complex was characterized in solution by IR and NMR (1H and 31P) spectroscopy and in the solid state by X-ray diffraction analysis. Re2(CO)7(bpcd)(μ-H)(η1-C CPh) crystallizes in the triclinic space group

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γ = 69.240(6)°, V = 2024.9(3) Å3, Z = 2, dcalc = 1.862 g cm−3 R = 0.0221, Rw = 0.243 for 4066 observed reflections. The bpcd ligand in 1 adopts a chelating mode with a linear phenylacetylide ligand being located on the adjacent rhenium center cis to the bpcd ligand. This complex represents the first structurally characterized example of a hydrido-bridged dirhenium complex possessing both a linear acetylide ligand and a chelating diphosphine ligand.  相似文献   

17.
The dinuclear Pt---Si complex {(Ph3P)Pt{μ-η2-H---SiH(IMP)]}2 (trans-1a–cis-1b=3:1; IMP=2-isopropyl-6-methylphenyl) reacted with basic phosphines such as 1,2-bis(diphenylphosphino)ethane (dppe) and dimethylphenylphosphine (PMe2Ph) to afford different dinuclear Pt---Si complexes with loss of H2, {(P)2Pt[μ-SiH(IMP)]}2 [P=dppe, trans-2a (major), cis-2b (trace); PMe2Ph, 3 (trans only)]. Complexes 2 and 3 were characterized by multinuclear NMR spectroscopy and X-ray crystallography (2a). In contrast, the reaction of 1a,b with the sterically demanding tricyclohexylphosphine (PCy3) afforded {(Cy3P)Pt{μ-η2-H---SiH(IMP)]}2 (trans-4a–cis-4b 2:1) analogous to 1a,b where the central Pt2Si2(μ-H)2 core remains intact but the PPh3 ligands have been replaced by PCy3. Complexes 4a and 4b was characterized by multinuclear NMR and IR spectroscopies.  相似文献   

18.
The 1,3-oxazine complexes cis- and trans-[PtCl2{ C(R)OCH2CH2C}H22] (cis: R=CH3 (1a), CH2CH3 (2a), (CH3)3C (3a), C6H5 (4a); trans:R =CH3 (1b), C6H5 (4b)) were obtained in 51-71% yield by reaction in THF at 0 °C of the corresponding nitrile complexes cis- and trans-[PtCl2(NCR)2] with 2 equiv. of −OCH2CH2CH2Cl, generated by deprotonation of 3-chloro-1-propanol with n-BuLi. The cationic nitrile complexes trans-[Pt(CF3)(NCR)(PPh3)2]BF4 (R=CH3, C6H5) react with 1 equiv, of − OCH2CH2CH2Cl to give a mixture of products, including the corresponding oxazine derivatives trans-[Pt(CF3){ CH2}(PPh3)2]BF4 (5 and 6), the chloro complex trans- [Pt(CF3)Cl(PPh3)2] and free oxazine H2. For short reaction times (c. 5–15 min) the oxazine complexes 5 and 6 could be isolated in modest yield (37–49%) from the reaction mixtures and they could be separated from the corresponding chloro complex (yield 40%) by taking advantage of the higher solubility of the latter derivative in benzene. For longer reaction times (> 2 h), trans-[Pt(CF3)Cl(PPh3)2] was the only isolated product. Complex 6 was crystallographically characterized and it was found to contain also crystals of trans- [PtCl{ H2}(PPh3)2]BF4, which prevented a more detailed analysis of the bond lengths and angles within the metal coordination sphere. The 1,3-oxazine ring, which shows an overall planar arrangement, is characterized by high thermal values of the carbon atoms of the methylene groups indicative of disordering in this part of the molecule in agreement with fast dynamic ring processes suggested on the basis of 1H NMR spectra. It crystallizes in the trigonal space group P , with a=22.590(4), b=15.970(3) Å, γ=120°, V=7058(1) Å3 and Z=6. The structure was refined to R=0.059 for 3903 unique observed (I3σ(I)) reflections. A mechanism is proposed for the conversion of nitrile ligands to oxazines in Pt(II) complexes.  相似文献   

19.
Analogy with the isolable oxo cluster [Fe3(CO)9(μ3-O)]2−, which is structurally interesting and synthetically useful, prompted the present attempt to synthesize its ruthenium analog. Although the high reactivity of [Ru3(CO)9(μ3-O)]2− (I) prevented its isolation, the reaction of this species with [M(CO)3(NCCH3)]+, where M = Mn or Re, yields [PPN][MRu3(CO)12(η2-μ3-NC(μ-O)CH3]−. The high nucleophilicity of the oxo ligand in [Ru3(CO)9(μ3-O)]2− (I) appears to be responsible for the conversion of acetonitrile to an acetamidediato ligand and for the instability of I. The crystal structure of [PPN][MnRu3(CO)12(η2-μ3-NC(μ-O)CH3)]] reveals a hinged butterfly array of metal atoms in which the acetamidediato ligand bridges the two wings with μ3-N bonding to an Mn and two Ru atoms, and μ-O bonding to an Ru atom.  相似文献   

20.
The water-soluble bisphosphine, 1,2-bis(bis(hydroxymethyl)phosphino)ethane (1), was synthesized in near quantitative yield by the reaction of bisphosphine, H2PCH2CH2PH2, with an aqueous formaldehyde in the presence of K2PtCl4. The reaction of this water-soluble bisphosphine 1 with cis-Pt(COD)Cl2 affords the mononuclear bischelate complex, [Pt{(HOH2C)2PCH2CH2P(CH2OH)2}2](Cl)2 (2), in near quantitative yield. The new ligand and complex have been characterized spectroscopically and the structure of the metal complex, 2, was determined by X-ray crystallography. The Pt(II) complex 2 crystallizes in the orthorhombic space group Pbca(a=14.623(1), B=16.216(2), C=9.319(4) Å) with Z=4. The final R value is 0.024.  相似文献   

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