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1.
[W 3Se 7(S 2P(OEt) 2) 3]Br was prepared by reacting (Et 4N) 2W 3Se 7Br 6 with KS 2P (OEt) 2 in CH 3CN and its crystal structure determined. In the [W 3(μ 3-Se)(μ 2-Se 2) 3] 4+ core the W---W bond length is 2.755(5)-2.764(6) Å and the Se---Se bond length is 2.32(1)- 2.34(4) Å. 相似文献
2.
Reactions between thiomolybdate or thiotungstate [Et 4N] 2[MS 4] (M = Mo, W) and CuSBu t led to the formation of two novel Mo(W)/Cu/S clusters [Et 4N] 4[{MS 4Cu 2(μ-SBu t)} 4] (1, M = Mo; 2, M = W). Single-crystal X-ray diffraction studies reveal that 2 is the first example of a molecular square containing CuS 2WS 2Cu building blocks. The reactions of [Et 4N] 2[MS 4] with CuCl followed by the addition of K 2SSS (SSS = 1,3,4-thiadiazole-2,5-dithiolate) yielded novel polymers {[Et 4N] 2[MS 4Cu 2(SSS)]} n (3, M = Mo; 4, M = W). Crystal structure determination shows that the CuS 2WS 2Cu building blocks in the anion of 4 are bridged by SSS 2− ligands to produce a helical chain running down the crystallographic b axis. 相似文献
3.
The reaction of Pt(PPh 3) n ( n = 3 or 4) with [(CF 3) 3Ge] 2Hg or (CF 3) 3GeHgPt(PPh 3) 2Ge(CF 3) 3 (I) gives a stable diplatinum complex [(CF 3) 3GePt(PPh 3) 2] 2Hg (II). X-Ray analysis has established that compound II contains a Ge---Pt---Hg---Pt---Ge chain of C2 symmetry. Both of the Pt atoms have distorted square-planar coordinations. The bond lengths are: Pt---Hg, 2.630(2) and 2.665(2) Å; Ge---Pt, 2.410(4) and 2.407(4) Å. Compound II reacts with dihydrogen in THF solution under mild conditions to give mercury and the hydride (CF3)3GePt(PPh3)2H. On interaction of II with R2Hg organomercurials (R = Cl, Et, GeEt3, Ge(CF3)3, Ge(C6F5)3) an unknown reaction takes place: Pt(PPh3)2 moieties migrate from the polymetallic grouping into the substrate with the formation of the corresponding RHgPt(PPh3)2R complexes or their demercuration products, R2Pt(PPh3);, (R = Cl, Et). The latter react further with complex I formed in the first step of the process to give Hg and (CF3)3GePt(PPh3)2R. The reaction schemes are discussed. 相似文献
4.
The binuclear molybdenum(II) complexes [Mo 2(O 2CCF 3) 4(PR 3) 2] (R = Ph, Et) act as templates for the self-condensation of 2-aminobenzaldehyde to give a new class of complexes in which a hydride ion bridges two molybdenum(III) centres, each of which carries a tetradentate macrocyclic ligand (C). The new hydrido complexes [Mo 2(C) 2 (H)(O 2CCF 3) 3(PPh 3) 2] (I), [Mo 2(C) 2(H) 2(O 2CCF 3) 2(PPh 3) 2] (II), and [Mo 2(C) 2 (H) 2(O 2CCF 3) 2(PEt 3) 2] 2 (V) exist in two or more isomeric forms as shown by their IR, 1H, 31P and 19F NMR spectra. Substitution with thiocyanate, nitrate and tetraphenylborate anions gives the new products [Mo 2(C) 2(H)(CO)(NCS) 3(PPh 3) 2] (III), [Mo 2(C) 2 (H) 2(O 2CCF 3)(NO 3)(PPh 3) 2] (IV), [Mo 2(C) 2(H)(O 2CCF 3)(PPh 3) 2](BPh 4) 2 (VI) and [Mo 2(C) 2(H) 2(O 2CCF 3)(PEt 3) 2](BPh 4) (VII), which also exist in isomeric forms. 相似文献
5.
The new terminal phosphinidene complex [Cp 2Zr=PDmp(PMe 3)] (Dmp=2,6-Mes 2C 6H 3; 1) was prepared in 81% yield by the reaction of [Li(Et 2O)][P(H)Dmp] with [Cp 2Zr(Me)Cl] in the presence of excess PMe 3. Compound 1 reacts with Ph 2PCl to produce selectively the sterically congested triphosphane DmpP(PPh 2) 2 (2) and [Cp 2ZrCl 2] in high yields. The structure of 2 obtained by X-ray diffraction analysis of a single crystal reveals phosphorus–phosphorus bond lengths of 2.251(2) and 2.234(2) Å and a PPP bond angle of 105.46(6)°. 相似文献
6.
The adducts of O 2 and SO 2 with trans-MeOIr(CO)(PPh 3) 2 are formed in equilibria and have been characterized. Reaction of the SO 2 adduct, Ir(OMe)(SO 2)(CO)(PPh 3) 2 with dioxygen leads to the sulfato complex, Ir(Ome)(CO)(PPh 3) 2(SO 4), the structure of which has been determined. Ir(Ome)(CO)(PPh 3) 2(SO 4) crystallizes in the monoclinic system with a 11.958(2), b 14.163(3), c 12.231(2) Å, β 118.365(12)°, V 1822.7(6) Å 3 and Z = 2. Diffraction data for 2θ = 4.5–45.0° (Mo- K) were collected with a Syntex P2 1 diffractometer and the structure was solved (assuming space group P2 1/ m and an unpleasant 2-fold disordered model) and refined to R = 4.8% for all 2512 independent data ( R = 3.5% for those 2042 data with ¦F O¦ > 6σ(¦ F¦)). The iridium(III) atom has a distorted octahedral coordination sphere with trans PPh 3 ligands and a cis-chelating bidentate O, O′-SO 4 group; the structure is completed by mutually cis OMe and CO ligands. 相似文献
7.
Three tetranuclear clusters [Ru 4H 4(CO) 11(PPh 3)] (1), [Ru 4H 2(CO) 12(PPh 3)] (2) and [Ru 3IrH(CO) 12(PPh 3)] (3) were formed in the reaction of [Ir(CO)Cl(PPh 3) 2] and Na[Ru 3H(CO) 11] in tetrahydrofuran. Complexes 1–3 were characterized by IR and 1H and 31P NMR, and the structure of the clusters was confirmed by single crystal X-ray analysis. In 2 and 3 one of the carbonyls bridges between two ruthenium atoms; otherwise the compounds contain only terminal carbonyls. 相似文献
8.
The reactions of the diruthenium carbonyl complexes [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)]X (X=BF 4− (1a) or PF 6− (1b)) with neutral or anionic bidentate ligands (L,L) afford a series of the diruthenium bridging carbonyl complexes [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-(L,L)) 2]X n ((L,L)=acetate (O 2CMe), 2,2′-bipyridine (bpy), acetylacetonate (acac), 8-quinolinolate (quin); n=0, 1, 2). Apparently with coordination of the bidentate ligands, the bound acetate ligand of [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)] + either migrates within the same complex or into a different one, or is simply replaced. The reaction of [Ru 2(μ-dppm) 2(CO) 4(μ,η 2-O 2CMe)] + (1) with 2,2′-bipyridine produces [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe) 2] (2), [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe)(η 2-bpy)] + (3), and [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-bpy) 2] 2+ (4). Alternatively compound 2 can be prepared from the reaction of 1a with MeCO 2H–Et 3N, while compound 4 can be obtained from the reaction of 3 with bpy. The reaction of 1b with acetylacetone–Et 3N produces [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-O 2CMe)(η 2-acac)] (5) and [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-acac) 2] (6). Compound 2 can also react with acetylacetone–Et 3N to produce 6. Surprisingly [Ru 2(μ-dppm) 2(μ-CO) 2(η 2-quin) 2] (7) was obtained stereospecifically as the only one product from the reaction of 1b with 8-quinolinol–Et 3N. The structure of 7 has been established by X-ray crystallography and found to adopt a cis geometry. Further, the stereospecific reaction is probably caused by the second-sphere π–π face-to-face stacking interactions between the phenyl rings of dppm and the electron-deficient six-membered ring moiety of the bound quinolinate (i.e. the N-included six-membered ring) in 7. The presence of such interactions is indeed supported by an observed charge-transfer band in a UV–vis spectrum. 相似文献
9.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
10.
The product isolated from the reaction of (μ-H) 2Os 3(CO) 9(PPh 3) with ethylene is shown to be the ethylidene complex (μ-H) 2Os 3(CO) 9(PPh 3)(μ-CHCH 3) (1) rather than the ethylene complex (μ-H)(H)Os 3(CO) 9(PPh 3)(C 2H 4), as previously claimed. The characterization of 1 is based on a combination of 1H and 13C NMR results. The 1H NMR data (δ 6.84 (1 H D), 2.53 (3 H C), J(CD) = 7.4 Hz) establish the presence of the ethylidene moiety, whereas detailed analysis of the 1-D and 2-D 13C NMR spectra of 13CO-enriched 1 indicates the relative positions of the ethylidene, hydride, and phosphine ligands on the triosmium framework. 相似文献
11.
The reaction of K[ReH 6(PPh 3) 2] with [RhCl(CO)L 2] [L= PPh 3, 1,2,5-triphenylphosphole (TPP), or P(OMe) 3] leads to the new electronically unsaturated heterobimetallic polyhydride complexes [(CO)(PPh 3) 2HRe(μ-H) 3RhL 2] in moderate-to-good yields. The structures of these complexes have been established on the basis of spectroscopic data, especially 1H and 31P NMR. The bridging hydride ligands are fluxional but there is either a slow or nonexistent exchange between terminal and bridging hydrides. For L = PPh 3 or TPP, protonation with tetrafluoroboric acid affords quantitatively the cationic complexes [(CO)(PPh 3) 2HRe(μ-H) 3RhHL 2] +, isolated as the BF 4− or the BPh 4− salts. 相似文献
12.
Dehydrocoupling reactions of primary amines RNH 2 with PhSiH 3 were catalyzed by [(Et 2N) 3U][BPh 4] to give the corresponding aminosilanes PhSiH 3−n(NHR) n ( n=1–3), the relative yields of the products were found to be dependent on the experimental conditions and on the nature of R. For a primary silane (PhSiH 3), the reactivity of RNH 2 follows the order primary>secondary>tertiary. Similar dehydrocoupling reactions using secondary amines with secondary silanes were found to be less reactive. Homodehydrocoupling of the silane was found not to be a competing reaction at room temperature. The hydride [(RNH) 2UH][BPh 4], which is plausibly formed in the reaction of [(RNH) 3U][BPh 4] with PhSiH 3 is a likely intermediate in the catalytic cycle. 相似文献
13.
Reaction of Hg(S 7N) 2 with cis- PtCl 2(PR 3) 2 (PR 3 = PPh 3, PPh 2Me, PPHMe 2, PEt 3) in the presence of Na[PF 6] gives [Pt(S 3N)(PR 3) 2][PF 6] in 32–46% yield. The complexes have been characterized by IR, NMR and microanalyses. The X-ray crystal structures of two examples (PR 3 = PPh 2Me and PEt 3) show that the S 3N − ligand coordinates in a bidentate fashion via two sulphur atoms. 相似文献
14.
The reaction of [(CO)PPh 3) 2Re(μ-H) 2(μ-NCHPh)Ru(PPh 3) 2(PhCN)] (2) with HBF 4-Me 2O generates [(CO)PPh 3) 2Re(μ- H) 2(μ,η 1,η 2HNCHPh)Ru(PPh 3) 2(PhCN)][BF 4] (3). Monitoring the reaction by NMR spectroscopy shows the intermediate formation of [(CO)(PPh 3) 2 HRe(μ-H) 2(μ-NCHPh)Ru(PPh 3) 2(PhCN)][BF 4] (4). Attempted reduction of the imine ligand by a nucleophile (H − or CN −) failed, regenerating 2. Under dihydrogen at 50 atm, 3 is slowly transformed into [(CO)(PPh 3) 2HRe(μ-H) 3Ru(PPh 3) 2(PhCN)][BF 4] (5) with liberation of benzyl amine. 相似文献
15.
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl 2(P-P)] (P-P = (PPh 3) 2, Ph 2P(CH 2) 3PPh 2, Phd 2P(CH 2) 4PPh 2; 1,4-dithiols = HS(CH 2) 4SH, (−)DIOSH 2 (2,3- O-isopropylidene-1,4-dithiol-l-threitol), BINASH 2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt 3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph 2P(CH 2) 3PPh 2, Ph 2P(CH 2) 4PPh 2; dithiolato = −S(CH 2) 4S −, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh 3) 2] and [Pd(S(CH 2) 4S)(Ph 2P(CH 2) 3PPh 2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC1 2 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl 2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%. 相似文献
16.
A study has been carried out of the catalytic activity of the systems formed by [HRh{P(OPh) 3} 4] or [HRh(CO){P(OPh) 3} 3] with the modifying ligands P(OPh) 3, PPh 3, diphos and Cp 2Zr(CH 2PPh 2) 2 in hydroformylation of hex-1-ene (at p = 5 bar). The best results were obtained with the system [HRh{P(OPh) 3} 4]+Cp 2Zr(CH 2PPh 2) 2 (75–85% yeild of aldehydes). 相似文献
17.
Heterotrimetallic complexes with a Pt---Hg---Pt arrangement are formed by reaction of zerovalent platinum complexes with [(PPh 3) 2RPt---HgR]; X-ray diffraction has established the structure of [(PPh 3) 2(2,4,6-C 6H 2Cl 3)Pt] 2Hg. 相似文献
18.
Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C 5H 5)CH 2(2-C 4H 3NH) (2) with Ti(NMe 2) 4 affords bis(dimethylamido)titanium complex [(η 5-C 5H 4)CH 2(2-C 4H 3N)]Ti(NMe 2) 2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH 2(2-C 4H 3NH)} 2C 5H 4 (4), undergoes an analogous reaction with Ti(NMe 2) 4 to give [1,3-{CH 2(2-C 4H 3N)} 2(η 5-C 5H 3)]Ti(NMe 2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
19.
Polymerizations of ethylene have been carried out by using Cp 2*Zr(NMe 2) 2 (Cp *=C 5Me 5) compound combined with common alkyl aluminums (AlR 3) and methylaluminoxane (MAO) as cocatalysts. The AlMe 3 cocatalyzed system showed no activity due to the formation of stable but inactive heterodinuclear [Cp 2*2Zr(μ-Me) 2AlMe 2] + cations; however, the bulkier AlR 3 [AlEt 3, Al( i-Bu) 3 and Al( i-Bu) 2H] cocatalyzed systems showed very high activities. Especially, Cp 2*Zr(NMe 2) 2/Al( i-Bu) 3 catalyst showed higher catalytic activity and produced higher molecular weight (MW) polymer than Cp 2*Zr(NMe 2) 2/MAO catalyst, demonstrating both MAO and bulky AlR 3 are effective cocatalysts for Cp 2*Zr(NMe 2) 2 compound. 相似文献
20.
Reaction of trans-[ReCl(CNR)(dppe) 2] (R = Me (Ia) or tBu (Ib); DPPE = Ph 2PCH 2CH 2PPh 2) in CH 2Cl 2 with cynamide in the presence of TlBF 4 forms the new cynamide-isocyanide complexes trans-[Re(CNR)(NCNH 2)(dppe) 2][BF 4] (R = Me (IIa) or tBu (IIb)), which upon treatment by tBuOK or Et 3N give trans-[Re(NCNH)(CNR)(dppe) 2] (R = Me (IIIa) or tBu (IIIb)). The electrochemical behaviour of these species was studied by cyclic voltammetry and controlled potential electrolysis at a Pt electrode in an aprotic solvent, and cathodic reduction of II results in the formation of III. 相似文献
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