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1.
Reaction of the ligand-bridged derivatives [M3(CO)10{μ-(RO)2PN(Et)P(OR)2}] and [M3(CO)8{μ-(RO)2PN(Et)P(OR)2}2] (M = Ru or Os; R = Me or Pri) with halogens leads to the formation of cationic products [M3(μ-X)(CO)10{μ- (RO)2PN(Et)P(OR)2}]+ and [M3(μ-X)(CO)8{μ-(RO)2PN(Et)P(OR)2}2]+ (X = Cl, Br or I) in which the halogen bridges an opened edge of the metal atom framework; the crystal structure of [Ru3(μ-I)(CO)8{μ-(MeO)2PN(Et)P(OMe)2}2]PF6 is reported.  相似文献   

2.
A decanuclear silver chalcogenide cluster, [Ag10(Se){Se2P(OiPr)2}8] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag7(H){Se2P(OiPr)2}6], under thermal condition. The time-dependent NMR spectroscopy showed that 2 was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [CuxAg10-x(Se){Se2P(OiPr)2}8] (x = 0–7, 3), via heating [CuxAg7−x(H){Se2P(OiPr)2}6] (x = 1–6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical [Ag10(Se){Se2P(OiPr)2}8] structures in the asymmetric unit, a co-crystal of [Cu3Ag7(Se){Se2P(OiPr)2}8]0.6[Cu4Ag6(Se){Se2P(OiPr)2}8]0.4 ([3a]0.6[3b]0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, [3a]0.6[3b]0.4 and the previous published [Ag10(Se){Se2P(OEt)2}8] (1) are quite similar (10 metals, 1 Se2−, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism.  相似文献   

3.
The reactions of SnMe3Cl with salts of the cluster anionic complexes [Re6Q8(CN)6]4? (Q = S, Se) gave novel complexes [{(SnMe3)2(OH)}2{SnMe3}2{Re6S8(CN)6}] (I), (Me4N)2[{SnMe3(H2O)}2{Re6Se8(CN)6}] (II), [{(SnMe2)4(μ3-O)}2{Re6Se8(CN)6}] (III), and [(SnMe2)4(μ3-O)2(μ2-OH)2(H2O)2][{SnMe3 2{Re6Se8(CN)6}] (IV). The structures of I–IV were determined by X-ray diffraction. Compounds I, IV have the chain structures with the CN-SnMe3-NC bridges between the cluster anions [Re6Q8(CN)6]4?. Compound II contains isolated fragments {SnMe3(H2O)}2{Re6Se8(CN)6}2?. In the polymer framework of compound III, the cluster anionic complexes [Re6Se8(CN)6]4? are bound by the complex cations [(SnMe2)4(μ3-O)2]4+ formed due to the hydrolysis of the initial (SnMe3)Cl.  相似文献   

4.
The novel coordination polymers, [{Mn(DMF)3}2{Re6S8(CN)6}] (I), [{Mn(DMF)2(H2O)}2{Re6S8(CN)6}] · 2DMF (II), [{Mn(DMF)3}2{Re6Se8(CN)6}] (III), [{Mn(DMF)2(H2O)}2{Re6Se8(CN)6}] · 2DMF (IV), and [{Mn(DMF)2(H2O)}2{Re6Te8(CN)6}] · 2DMF (V), were synthesized by interaction of the octahedral cluster complexes [Re6(μ3-Q)8(CN)6]4? (Q = S, Se, Te) with the Mn2+ cations in the H2O-DMF mixture. The crystal structures of compounds I, II, IV, and V were determined by X-ray diffraction analysis. The structural analogies between mononuclear cyanometallates and the obtained cluster coordination polymers were discussed.  相似文献   

5.
Dissolution of [Fe2(μ-CO)(CO)4{μ-(RO)2PN(Et)P(OR)2}2] (R = Me, Pri or Ph) and [Ru2(μ-CO)(CO)4{μ-(RO)2PN(Et)P(OR)2}2](R = Me or Pri) in CCl4 leads to the rapid formation of [Fe2(μ-Cl)(CO)4 {μ-(RO)2PN(Et)P(OR)2}2]Cl and [Ru2Cl2(CO)4 {μ-(RO)2 PN(Et)P(OR)2}2], respectively, with the latter isomerising in dichloromethane or chloroform solution to [Ru2(μ-Cl)(Cl(CO)4{μ-(RO)2PN(Et)P(OR)2}2]Cl, which in turn decarbonylates to [Ru2(μ-Cl)Cl(CO)3{μ-(RO)2PN(Et)P(OR)2}2]; the structure of [Ru2Cl2(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2] has been established X-ray crystallographically.  相似文献   

6.
The ligand tetrakis(diphenylphosphinomethyl)methane, tpmm, binds in a η2, η2- bridging mode to square planar platinum(II) or palladium(II) centers to give complexes such as [Pt2Me4(μ-tpmm)] or [Pd2Cl4(μ-tpmm)]. These complexes yielded triflate derivatives [Pt2Me2(OTf)2(μ-tpmm)] or [Pd2(OTf)4(μ-tpmm)], and displacement of triflate by a bipyridine ligand then gave the cationic polymers [{Pt2Me2(μ-LL)(μ-tpmm)}n]2n+ or the cationic network materials [{Pd2(μ-LL)2(μ-tpmm)}n]4n+, LL=4,4’-bipyridine or 1,3-C6H4(CONH-4-C5H4N)2. Ligand tpmm reacts with copper(I) iodide to give [Cu4I4(μ-tpmm)2] or with silver(I) triflate to give [Ag2(OTf)2(μ-tpmm)], which then reacts with LL=1,3-C6H4(CONH-4-C5H4N)2 to give the polymeric complex [{Ag2(μ-LL)(μ-tpmm)}n]2n+. The structure determination of [Cu4I4(μ-tpmm)2] shows that it contains two isomeric forms with the tpmm ligands in either the η2, η2- or η3, η1- bridging mode.  相似文献   

7.
The new Mo/Se clusters [Mo3(μ3-Se)(μ2-Se2)3{N(SePPh2)2}3]Br (1) and [Mo3(μ3-Se)(μ2-Se2)3{Se2P(OCH2CH3)2}3]Br (2) have been synthesized by the selective substitution of the bromo ligands in the starting material [PPh4]2[Mo3(μ3-Se)(μ2-Se2)3Br6] with the selenoorgano bidentate ligands [N(SePPh2)2]– and [Se2P(OEt)2]–. The complexes have been characterized in solution by 31P- and 77Se-NMR spectroscopy and in the solid state by single crystal X-ray diffraction; the same cation structures are present both in solution and in the solid state. Crystallographic data for 1: [Mo3(μ3-Se)(μ2-Se2)3{N(SePPh2)2}3]Br·3 CH2Cl2, C72H60BrMo3N3P6Se13·3 CH2Cl2, trigonal, space group R3, a=21.299 (10) Å, c=38.433 (27) Å, V=15 100 (15) Å3, T=−120 °C, Z=6; crystallographic data for 2: Mo3(μ3-Se)(μ2-Se2)3{Se2P(OCH2CH3)2}3]Br, C12H30BrMo3P3O3Se13, monoclinic, space group P21/n, a=13.404 (2) Å, b=22.732 (4) Å, c=13.932 (3) Å, β=113.134 (3)°, V=3 903.7(12) Å3, T=−120 °C, Z=4. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASphosphine ligands / amine ligands / phosphate ligands / selenium / molybdenum cluster / 77Se-NMR spectroscopy  相似文献   

8.
The versatile coordination behavior of the P4 butterfly complex [{Cp*Cr(CO)3}2(μ,η1:1-P4)] ( 1 ) towards Lewis acidic pentacarbonyl compounds of Cr, Mo and W is reported. The reaction of 1 with [W(CO)4(nbd)] (nbd=norbornadiene) yields the complex [{Cp*Cr(CO)3}2(μ3,η1:1:1:1-P4){W(CO)4}] ( 2 ) in which 1 serves as a chelating P4 butterfly ligand. In contrast, reactions of 1 with [M(CO)4(nbd)] (M=Cr ( a ), Mo ( b )) result in the step-wise formation of [{Cp*Cr(CO)2}2(μ3,η3:1:1-P4){M(CO)5}] ( 3 a,b ) and [{Cp*Cr(CO)2}2-(μ4,η3:1:1:1-P4){M(CO)5}2] ( 4 a,b ) which contain a folded cyclo-P4 unit. Complex 4 a undergoes an unprecedented P1/P3-fragmentation yielding the cyclo-P3 complex [Cp*Cr(CO)2(η3-P3)] ( 5 ) and the as yet unknown phosphinidene complex [Cp*Cr(CO)2{Cr(CO)5}2(μ3-P)] ( 6 ). The identity of 6 is confirmed by spectroscopic methods and by the in situ formation of [{Cp*Cr(CO)2(tBuNC)}P{Cr(CO)5}2(tBuNC)] ( 7 ). DFT calculations throw light on the bonding situation of the reported products.  相似文献   

9.
The [{Mn(H2O)3}2{Re6Se8(CN)6}] · 3.3H2O complex was produced on slow evaporation of an aqueous solution containing the salt of a cluster complex K4Re6Se8(CN)6 · 3.5H2O and a 23-fold excess of Mn2+. The cluster complexes [Re6Se8(CN)6]4– are linked in a crystal into the charged coordination layers [{Mn(H2O)3}4{Re6Se8(CN)6}3]4– 2 through the Mn2+ cations. The Mn2+ cations are coordinated in a layer by three cyano nitrogen atoms of the cluster complexes; the Mn–N bond lengths are 2.13(4) and 2.21(2) Å. Each [Re6Se8(CN)6]4– anion is bonded to three manganese cations Mn(1). The anions are bonded additionally to the Mn(2) cations disordered over two close positions.  相似文献   

10.
The first atomically and structurally precise silver‐nanoclusters stabilized by Se‐donor ligands, [Ag20{Se2P(OiPr)2}12] ( 3 ) and [Ag21{Se2P(OEt)2}12]+( 4 ), were isolated by ligand replacement reaction of [Ag20{S2P(Oi Pr)2}12] ( 1 ) and [Ag21{S2P(Oi Pr)2}12]+ ( 2 ), respectively. Furthermore, doping reactions of 4 with Au(PPh3)Cl resulted in the formation of [AuAg20{Se2P(OEt)2}12]+ ( 5 ). Structures of 3 , 4 , and 5 were determined by single‐crystal X‐ray diffraction. The anatomy of cluster 3 with an Ag20 core having C 3 symmetry is very similar to that of its dithiophosphate analogue 1 . Clusters 4 and 5 exhibit an Ag21 and Au@Ag20 core of Oh symmetry composed of eight silver capping atoms in a cubic arrangement and encapsulating an Ag13 and Au@Ag12 centered icosahedron, respectively. Both ligand exchange and heteroatom doping result in significant changes in optical and emissive properties for chalcogen‐passivated silver nanoparticles, which have been theoretically confirmed as 8‐electron superatoms.  相似文献   

11.
Reaction of [Ru3(CO)12] with a two molar proportion of (RO)2PN(Et)P(OR)2 (R = Me or Pri) in benzene under reflux affords a number of products including [Ru3(CO)10{μ-(RO)2PN(Et)P(OR)2}], [Ru3(CO)9{μ-(RO)2PN(Et)P(OR)2}{η1-(RO)2PN(Et)P(OR)2}] and, as the major species, the tetranuclear derivative [Ru4(μ3-η2-CO)(CO)9{μ-(RO)2PN(Et)P(OR)2}2]. An X-ray diffraction study of [Ru4(μ3-η2-CO)(CO)9{μ-(MeO)2PN(Et)P(OMe)2}2] has revealed that the skeletal framework adopts a butterfly structure and that one of the carbonyl groups functions as a triply bridging four-electron donor ligand capping the two wing-tip and one of the hinge ruthenium atoms.  相似文献   

12.
Copper and Silver Clusters with Bridging Imido and Amido Ligands From the reactions of copper and silver chloride with tertiary phosphines and lithiated aniline the compounds [{Li(dme)3}4][Cu18(NPh)11] ( 1 ) and [Ag6(NHPh)4(PnPr3)6Cl2] ( 2 ) were obtained. The structure of the anion in 1 is closely related to the structures of the reported clusters [Cu12(NPh)8]4– [1] and [Cu24(NPh)14]4– [2]: 1 represents the third phenyl imido bridged copper cluster which contains parallel Cu3‐ and Cu6‐planes. The dimeric compound 2 consists of two Ag3 units with bridging phenyl amido ligands. Two chloride and six phosphine ligands complete the ligand sphere and shield the metal core effectively.  相似文献   

13.
Treatment of [Ru2(μ-CO)(CO)4{μ-(RO)2PN(Et)P(OR)2}2] (R = Me or Pri), electron-rich derivatives of [Ru2(CO)9], with a twice molar amount of a silver(I) salt in aprotic, weakly co-ordinating solvents such as acetone, acetonitrile or benzonitrile leads to the formation of the solvento species [Ru2(CO)5(solvent)- {μ-(RO)2PN(Et)P(OR)2}2]2+. The structure of the benzonitrile derivative, [Ru2(CO)5(PhCN){μ-(PriO)2PN(Et)P(OPri)2}2](SbF6)2, has been established by X-ray crystallography. The acetone molecule in [Ru2(CO)5(acetone){μ- (RO)2PN(Et)P(OR)2}2]2+ is readily replaced by various nucleophiles to afford products of the type [Ru2(CO)5L{μ-(RO)2PN(Et)P(OR)2}2]2+, where L is a neutral ligand such as CO, Me2C6H3NC, PhCN, C5H5N, H2O, Me2S or SC4H8, [Ru2Y(CO)5{μ-(RO)2PN(Et)P(OR)2}2]2+, where Y− is an anionic ligand such as Cl−, Br−, I−, CN−, SCN−, MeCO2−, CF3CO2− or [Ru2(μ-Y)(CO)4{μ-(RO)2- PN(Et)P(OR)2}2]+ where Y− is an anionic ligand such as Cl−, Br−, I−, SPh−, S2CNEt2−, MeCO2− or CF3CO2−.  相似文献   

14.
In the reaction of Na2Se with [Fe(CO)5] in isopropanol with subsequent acidification with HCl, which is used to synthesize [(μ-H)2Fe3(μ3-Se)(CO)9] (II), the cluster [(μ-H)2Fe5(μ3-Se)2(CO)14] (I) was detected. In assumption that compound I could serve as a suitable synthon for preparing the bulky heterometallic clusters, its reactions with the Rh-containing complexes were studied. The reaction of I with [Rh(CO)2Cp*] (Cp* is pentamethylcyclopentadienyl) was found to give a mixture of the products. The main reaction products were isolated and their structures were determined: [Fe2Rh(μ3-Se)2(CO)6Cp*], [Fe2Rh(μ3-Se)(μ3-CO)(CO)6Cp*], [FeRh2(μ3-Se)(μ-CO)(CO)3Cp 2 * ], [Fe2Rh2(μ4-Se)(μ-CO)4(CO)2Cp 2 * ]. Potassium hydride treatment of II with subsequent addition of [Cp*Rh(CH3CN)3](CF3SO3)2 leads to the well-known cluster complex [Fe3Rh(μ4-Se)(CO)9Cp*]. A set of the reaction products indicates that the {Fe5Se2} core cannot be used as one-piece “building block” in the synthesis of heterometallic clusters.  相似文献   

15.
Reaction of [Ru2(μ-CO)(CO)4{μ-(RO)2PN(Et)(OR)2}2] (R = Me or Pri) with the protonic acids HCl, HBr, HNO3, H2BO2F, CF3COOH, PhSH/HPF6, and H2CO3/HPF6 produces [Ru2A(CO)5 {μ-(RO)2PN(Et)(OR)2}2]+ and/or [Ru2(μ-A)(CO)4{μ-(RO)2PN(Et)(OR)2}2]+ (A = Cl, Br, ON(O)O, OB(F)OH, OC(CF3)O, SPh, and OC(OH)O) via [Ru2H(CO)5{μ-(RO)2PN(Et)(OR)2}2]+ as intermediate; the structure of [Ru2{μ-OB(F)OH}(CO)4{-(PriO)2PN(Et)P(OPri)2}]+ has been established X-ray crystallographically.  相似文献   

16.
Reaction of [Fe2(CO)9] with a half molar amount of R2PYPR2 (Y = CH2, R = Ph, Me, OMe or OPri; Y = N(Et), R = OPh, OMe or OCH2; Y = N(Me), R = OPri or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe2(μ-CO)(CO)6{μ-R2PYPR2}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe2(μ-CO)(C))4{μ-R2PYPR2}2] but under thermal conditions in the formation of the mononuclear species [Fe(CO)3{R2PYPR2}]. Reaction of [Ru3(CO)12] with an equimolar amount of (RO)2PN(R′)P(OR)2 (R′ = Me, R = Pri or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru3(CO)10{μ-(RO)2PN(OR)2}] which reacts further with excess (RO)2PN(R′)P(OR)2 on irradiation with ultraviolet light to afford the dinuclear compound [Ru2(μ-CO)(CO4{μ-(RO)2PN(R′)P(OR)2}2]. The molecular structure of [Ru2(μ-CO)(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2], which has been determined by X-ray crystallography, is described.  相似文献   

17.
Reactions of Ru3(CO)12 with diphosphazane monoselenides Ph2PN(R)P(Se)Ph2 [R = (S)-∗CHMePh (L4), R = CHMe2 (L5)] yield mainly the selenium bicapped tetraruthenium clusters [Ru4(μ4-Se)2(μ-CO)(CO)8{μ-P,P-Ph2PN(R)PPh2}] (1, 3). The selenium monocapped triruthenium cluster [Ru3(μ3-Se)(μsb-CO)(CO)7{κ2-P,P-Ph2PN((S)-∗CHMePh)PPh2}] (2) is obtained only in the case of L4. An analogous reaction of the diphosphazane monosulfide (PhO)2PN(Me)P(S)(OPh)2 (L6) that bears a strong π-acceptor phosphorus shows a different reactivity pattern to yield the triruthenium clusters, [Ru3(μ3-S)(μ3-CO)(CO)7{μ-P,P-(PhO)2PN(Me)P(OPh)2}] (9) (single sulfur transfer product) and [Ru3(μ3-S)2(CO)5{κ2-P,P-(PhO)2PN(Me)P(OPh)2}{μ-P,P-(PhO)2PN(Me)P(OPh)2}] (10) (double sulfur transfer product). The reactions of diphosphazane dichalcogenides with Ru3(CO)12 yield the chalcogen bicapped tetraruthenium clusters [Ru4(μ4-E)2(μ-CO)(CO)8{μ-P,P-Ph2PN(R)PPh2}] [R = (S)-∗CHMePh, E = S (6); R = CHMe2, E = S (7); R = CHMe2, E = Se (3)]. Such a tetraruthenium cluster [Ru4(μ4-S)2(μ- CO)(CO)8{μ-P,P-(PhO)2PN(Me)P(OPh)2}] (11) is also obtained in small quantities during crystallization of cluster 9. The dynamic behavior of cluster 10 in solution is probed by NMR studies. The structural data for clusters 7, 9, 10 and 11 are compared and discussed.  相似文献   

18.
New Amido and Imido Bridged Complexes of Copper – Syntheses and Structures of [{Li(OEt2)}2][Cu(NPh2)3], [ClCuN(SnMe3)3], [{CuN(SnMe3)2}4], [Cu16(NH2tBu)12Cl16], [{CuNHtBu}8], [Li(dme)3][Cu6(NHMes)3(NMes)2], [PPh3(C6H4)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}2], and [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8] The reactions of stannylated and lithiated amines with coppersalts (halogenides, thiocyanates) lead to amido and imido bridged complexes which contain one to twelve metal atoms. [{Li(OEt2)}2][Cu(NPh2)3] ( 1 ) results from the reaction of CuCl with LiNPh2 in the presence of trimethylphosphine. With N(SnMe3)3, CuCl reacts to the donor‐acceptor complex [ClCuN(SnMe3)3] ( 2 ) that is transformed into the tetrameric complex [{CuN(SnMe3)2}4] ( 3 ) by thermolysis. 3 can also be obtained by the reaction of LiN(SnMe3)2 with Cu(SCN)2. While terminally bound in 1 , the amido ligand is μ2‐bridging between copper atoms in compound 3 . The influence of the alkyl amide's leaving group can be seen from a comparison of the reactivity of Me3SnNHtBu and LiNHtBu, respectively. With Me3SnNHtBu, CuCl2 forms the polymeric compound [Cu16(NH2tBu)12Cl16] ( 4 ) whereas in the case of LiNHtBu with both CuCl and CuSCN, the complex [{CuNHtBu}8] ( 5 ) is obtained. The latter contains two planar Cu4N4‐rings similar to those in 3 . If a mesityl group is introduced at the lithium amide, different products are accessible. Both, CuBr and CuSCN, lead to the formation of [Li(dme)3][Cu6(NHMes)3(NMes)2] ( 6 ) whose anion consists of a prismatic copper core with μ2‐bridging amido and μ3‐bridging imido ligands. In the presence of PPh4Cl, a mixture of Cu(SCN)2 and LiNHMes enables an ortho‐metallation reaction that produces [PPh3(C6H4)CuNHMes] ( 7 ). From the reaction of CuSCN with LiNHMes and LiNHPh either the dimeric complex [{[Li(dme)][Cu(NHMes)(NHPh)]}2] ( 8 ) or the cluster [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8] ( 9 ) results. The anion in 9 exhibits a cubo‐octahedron of copper atoms μ3‐bridged by (NPh)2–‐ligands. The solid state structures of compounds 1 – 9 have been determined by single crystal X‐ray diffraction.  相似文献   

19.
Assembly of Tetranuclear Ruthenium Complexes with Planar Metal Core by Condensation of Two Diruthenium Units Using Bridging Ligands: Synthesis and Molecular Structure of [Ru4(CO)8{μ2-P(Cy)2}4] and [Ru4(CO)8{μ4-P(Cy)}2{μ2}2](Cy = Cyclohexyl) The dinuclear complexes [Ru2(CO)6{μ-P(Cy)2}2] ( 1 ) or [Ru2(CO)4{μ-(HCO2)}2{P(Cy)2H}2] ( 2 ) react in THF solution at 160° to give the tetranuclear complexes [Ru4(CO)8{μ2-P(Cy)2}4] ( 3 ) and [Ru4(CO)8{μ4-P(Cy)}2{μ2-P(Cy)2}2] ( 4 ), as well as the trinuclear complex [Ru3(CO)7(μ2-H){μ2-P(Cy)2}3] ( 5 ). If the reaction is performed at 200°, the bicapped tetranuclear species 4 is obtained in a higher yield, whereas 3 and 5 are formed in trace amounts only. The phenyl derivatives [Ru2(CO)6{μ-P(Ph)2}2] ( 6 ) or [Ru2(CO)4{μ-(EtCO2)}2{P(Ph)2H}2] ( 7 ) react in a similar manner to give only the complex [Ru4(CO)8{μ4-P(Ph)}2{μ2-P(Ph)2}2] ( 8 ), analogous to 4 . The molecular structure of 3 consists of a planar framework of four Ru-atoms, each Ru—Ru bond being bridged by a μ2-dicyclohexylphosphino ligand. The complex 4 represents a planar rectangular Ru core, both faces being capped by μ4-cyclohexylphosphinidene ligands and two opposite edges being bridged by μ2-dicyclohexylphosphino ligands.  相似文献   

20.
The oxidative addition of 1-bromopropane to trans-[RhBr(CO){P(p-EtC6H4)3}2] has been found to follow pseudo first-order kinetics and give only an acylrhodium(III) product. The reaction is not catalysed by added bromide ion in chloroform solution, indicating that an anionic intermediate such as [RhBr2(CO){P(p-EtC6H4)3}]− does not play an important part in this reaction. The oxidative addition of iodomethane to trans-[Rh(μ-X)(CO)(PPh3)]2 (X  Cl and I) is pseudo first-order, the reactivity increasing on replacing chloride by iodide.  相似文献   

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