共查询到20条相似文献,搜索用时 15 毫秒
1.
Nigel J. Kermode Michael F. Lappert Brian W. Skelton Allan H. White John Holton 《Journal of organometallic chemistry》1982,228(3):C71-C75
The reaction of [Pt(PEt3)3] with CH2I2 affords trans-[Pt(CH2PEt3)I(PEt3)2]I and is believed to proceed via the α-functionalised alkyl cis-[Pt(CH2I)I(PEt3)2], because similar ylides are obtained from cis- or trans-[PT(CH2X)(PPh3)2X] (XCl, Br, or I) with PR3 (PEt3, PBu3n, PMePh2, PEtPh2, or PPh3); cis-[Pd(CH2I)-I(PPh3)2] does not react with excess PPh3, but with PEt3 yields trans-[Pd(CH2PEt3)I(PPh3)2]I; the X-ray structure of trans-[Pt(CH2PEt3)I(PEt3)2]I (current R = 0.045) shows PtP(1) 2.332(7), PtP(2) 2.341(8), PtC 2.08(2), and PtI 2.666(2) Å, and angles (a) C(1)PtI, P(1), P(2): 176.9(8), 91.6(6), 93.4(6), (b) IPtP(1), P(2): 87.1(2), 88.5(2), and (c) P(1)P(2), 166.8(3), and (d) PtC(1)P(3), 118(1)°. 相似文献
2.
Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes [PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of [PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave [PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave [Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with [PtX2{Ph2PCH(Me)PPh2}] gave [Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and [Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with [Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave [Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes [PtMe2(dpmMe)] or [Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph2PCH(Me)PPh2]. Treatment of [Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of [Ir(CO)(dpmMe)2]Cl with [Cu(C≡CPh)2], [AgCl(PPh3)] or [AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)2]Cl in CHCl3 gave [RhHCl(dpmMe)2]Cl. Recrystallization of [Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave [RhO2(dpmMe)2]BPh4. Treatment of [Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and [Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
3.
Thienylmercury(II)chloride reacts with [Pd(PPh3)2Cl2], [Pd(PPh3)4] and [Pt(PPh3)4] to afford new compounds containing a metal-2-thienyl linkage. The compound [Pd(PPh3)2(2-C4H3S)Cl] probably has trans stereochemistry.2-Bromothiophen undergoes oxidative addition with [Pd(PPh3)4] and [Pt(PPh3)4], probably via a radical mechanism. With [Pd(CO)(PPh3)3], a carbonyl inserted product is obtained. The bromo-metal(II) complexes have trans stereochemistry. The course of the reaction between 3-methyl-2-bromothiophen and Pd(PPh3)4 is more complex. Thus, there is evidence of some cis bromopalladium(II) compounds amongst the products, also there is good evidence to support the view that some isomerisation of 3-methyl-2-thienyl to 4-methyl-2-thienyl occurs during the reaction, thus giving greater molar quantities of [Pd(PPh3)2(4-CH3-2-C4H2S)Br] than can be accounted for from any initial 4-methyl-2-bromothiophen impurity.The metallation of the thiophen ring, probably in the 4-position, with palladium(II) is described for 3-theylidene-4-methylaniline. 相似文献
4.
O. V. Sizova Yu. S. Varshavskii L. V. Skripnikov 《Russian Journal of Coordination Chemistry》2007,33(5):313-322
The DFT B3LYP method was used to optimize the geometries, calculate the IR spectra, and analyze the electronic structures of carbonyl(carboxylato)(phosphine)rhodium(I) complexes, namely, trans-[Rh(Cl)(CO)(PPh3)2], trans-[Rh(OCOR)(CO)(PPh3)2] (R = H, CH3, and CF3), and trans-[Rh(OCOH)(CO)(PX3)2], and free PX3 molecules (X = H, F, CH3, i-Pr, Cy, and Ph). A linear correlation between v(CO) in the IR spectra of trans-[Rh(OCOH)(CO)(PX3)2] and the HOMO energy of the free PX3 molecule was found for phosphines with nonaromatic substituents X. It was concluded that the electronic state of the CO group is mainly determined by the σ-donor properties of phosphines. The distinctive features of the electronic structure of triphenylphosphine are discussed. 相似文献
5.
《Journal of organometallic chemistry》1994,476(1):C9-C11
Treatment of a THF solution of trans-[ReCl(N2)(dppe)2] (dppe = Ph2PCH2CH2PPh2) with NO, in the presence of Tl[BF4], forms trans-[Re(NO)2(dppe)2][BF4], a rare formal 20-electron d8-rhenium nitrosyl complex which, by reaction with HX (X = BF4, Cl or HSO4), gives trans-[ReF(NO)(dppe)2][BF4] (2) (the X-ray structure of which is reported) or trans-[ReX(NO)(dppe)2]X (3, X = Cl or HSO4), respectively, as well as nitrous oxide. 相似文献
6.
The reactions of [Ru(H)(Cl)(CO)(PPh3)3] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [RuII(dbsq)(Cl)(CO)(PPh3)2] and [RuII(tcsq)(Cl)(CO)(PPh3)2], respectively. The reaction of [Ru(H)2(CO)(PPh3)3] with tcq has furnished [RuII(tcsq)(H)(CO)(PPh3)2]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh3)2] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μB) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-31P atoms (Aiso17 G). The stretching frequency of the CO ligand increases by 20 cm−1 in going from [Ru(dbsq)(Cl)(CO)(PPh3)2] to [Ru(tcsq)(Cl)(CO)(PPh3)2] consistent with electron withdrawal by chloro substituents. For the same reason the E1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh3)2] and [Ru(tcsq)(Cl)(CO)(PPh3)2]. 相似文献
7.
《Journal of organometallic chemistry》1994,481(2):195-204
The reaction of K2[PtCl4] with 2-(1-methylbenzyl)pyridine, HL, and 2-benzylpyridine, HL', affords the cyclometallated species [{Pt(L)Cl}2] (1) and [{Pt(L')Cl}2] (2), respectively. The chloride bridge in complex 1 can be split by neutral or anionic species to give the monomeric, [Pt(L)(Ph3P)Cl], as two isomers, trans-P-Pt-C (3) and trans-P-Pt-N, (4), [Pt(L)(py)Cl] (5), [Pt(L)(CO)Cl] (6), [Pt(L)(CNCH2SO2C6H4CH3-4)Cl] (7), [Pt(L)(acac)] (Hacac = 2,4-pentanedione) (8), [Pt(L)(dppm)][BF4] (dppm = bis(diphenyl-phosphino)methane) (9), [Pt(L)(dppe)][BF4] (dppe = bis(diphenylphosphino)ethane) (10) and [Pt(L)(dipy)][BF4](dipy = 2,2'-dipyridine) (11). Similarly, compound 2, by reaction with Ph3P, affords [Pt(L')(Ph3P)Cl], as two isomers, trans-P-Pt-C (12) and trans-P-Pt-N (13). Reaction of compounds 1 or 4 with AgBF4 in acetonitrile affords [Pt(L)(CH3CN)2IBF4] (14) or [Pt(L)(Ph3P)-(CH3CN)][BF4] (15). From these, [Pt(L)(Ph3P)2][BF4] (16), [Pt(L)(Ph3P)(CO)][BF4] (17) and [Pt(L)(Ph3P)(py)][BF4] (18), can be obtained by displacement of the coordinated acetonitrile. The new complexes were characterized by IR, 1H and 31P NMR and FAB-MS spectroscopic techniques. The NMR spectra at room temperature of most of the species derived from HL give evidence for the presence in solution of two diastereomers a and b. The structure of one diastereomer of complex 4 has been solved by single crystal X-ray diffraction, 4b. The platinum atom is in an almost square planar geometry with a P-Pt-N trans arrangement: Pt-N = 2.095(3), Pt-C = 1.998(4), Pt-P = 2.226(1) and Pt-Cl = 2.400(1) Å. The six-membered cyclometallated ring is in a boat conformation, with the CH3 group in an equatorial position, i.e pointing away from the metal. Attempts to obtain [{Pt(L″)Cl}2] (HL″ = 2-(dimethylbenzyl)pyridine), afforded an insoluble product heavily contaminated by platinum metal; treatment of this crude material with Ph3P gave [Pt(L″)(Ph3P)Cl] (19). 相似文献
8.
Elizaveta P. Shestakova Aleksei B. Nikolskii 《Journal of organometallic chemistry》2005,690(14):3397-3404
Cationic methyl complex of rhodium(III), cis-[Rh(Acac)(PPh3)2(CH3)(Py)][BPh4] (1) as a single isomer with Py in the trans to PPh3 position, is formed upon the reaction of cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] with pyridine in methylene chloride solution.Complex 1 was characterized by elemental analysis and by 31P{1H} and 1H NMR spectra.Cationic pentacoordinate acetyl complexes, trans-[Rh(Acac)(PPh3)2(COCH3)][BPh4] (2) and trans-[Rh(BA)(PPh3)2(COCH3)][BPh4] (3), are prepared by action of carbon monoxide on cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] and cis-[Rh(BA)(PPh3)2(CH3)(CH3CN)][BPh4], respectively, in methylene chloride solutions.Complexes 2 and 3 were characterized by elemental analysis and by IR, 31P{1H}, 13C{1H} and 1H NMR. According to NMR data, 2 and 3 in solution are non-fluxional trigonal bipyramids with β-diketonate and acetyl ligands in the equatorial plane and axial phosphines.In solutions, 2 and 3 gradually isomerize into octahedral methyl carbonyl complexes trans-[Rh(Acac)(PPh3)2(CO)(CH3)][BPh4] (4) and trans-[Rh(BA)(PPh3)2(CO)(CH3)][BPh4] (5), respectively.Complexes 4 and 5 were characterized by IR, 31P{1H}, 13C{1H} and 1H NMR, without isolation.Upon the action of PPh3 on cis-[Rh(Acac)(PPh3)2(CH3)(CH3CN)][BPh4] and cis-[Rh(BA)(PPh3)2(CH3)(CH3CN)] [BPh4], reductive elimination of the methyl ligand as a phosphonium salt, [CH3PPh3][BPh4], occurs to give square planar rhodium(I) complexes [Rh(Acac)(PPh3)2] and[Rh(BA)(PPh3)2], respectively. The reaction products were identified in the reaction mixtures by 31P{1H} and 1H NMR. 相似文献
9.
《Journal of organometallic chemistry》1990,396(1):C22-C24
The reaction of the hydridometal complex [RuClH(CO)(PPh3)3] with 1,4-diphenyl-butadi-1,3-yne has been investigated and found to proceed with monoinsertion to give a coordinatively unsaturated σ-vinyl complex [Ru-{C(CCPh)CHPh} Cl(CO)(PPh3)2], which is also the major product of the reaction of [RuClH(CO) (PPh3)3] with [Hg(CCPh)2]. 相似文献
10.
Issam M. Gabr Hala A. El-Asmy Mohamed S. Emmam Sahar I. Mostafa 《Transition Metal Chemistry》2009,34(4):409-418
Synthetic procedures are described that allow access to the new complexes cis-[Mo2O5(apc)2], cis-[WO2(apc)2], trans-[UO2(apc)2], [Ru(apc)2(H2O)2], [Ru(PPh3)2(apc)2], [Rh(apc)3], [Rh(PPh3)2(apc)2]ClO4, [M(apc)2], [M(PPh3)2(apc)]Cl, [M(bpy)(apc)]Cl (M(II) = Pd, Pt), [Pd(bpy)(apc)Cl], [Ag(apc)(H2O)2] and [Ir(bpy)(Hapc)2]Cl3, where Hapc, is 3-aminopyrazine-2-carboxylic acid. These complexes were characterized by physico-chemical and spectroscopic
techniques. Both Hapc and several of its complexes display significant anticancer activity against Ehrlich ascites tumour cells (EAC) in albino mice. 相似文献
11.
Jwu-Ting Chen Yu-Sung Yeh Wen-Hwa Tzeng Tsang-Miao Huang Ming-Chu Cheng Geen-Hsiang Lee Yu Wang 《中国化学会会志》1991,38(6):573-580
Treatment of trans-Pt(COCOPh)(Cl)(PPh3)2 (1a) with AgBF4in THF led to the formation of a metastatic complex trans-[Pt(COCOPh)(THF)(PPh3)2](BF4) (2) which readily underwent ligand substitution to give a cationic aqua complex trans-[Pt(COCOPh)(OH2)(PPh3)2](BF4) (5a). Complex 5a has been characterized spectroscopically and crystallographically. Analogous reaction of trans-Pt(COCOOMe)(Cl)(PPh3)2 (1b) with Ag(CF3SO3) in dried CH2C12 was found first to yield a methoxyoxalyl triflato complextrans-Pt(COCOOMe)(OTf)(PPh3)2 (6). Attempts to crystallize the triflato product in CH2-cl2hexane under ambient conditions also afforded an aqua complex of the triflate salt f/wu-[Pt(COCOOMe)(OH2)(PPhj)2](CF3SO3) (5b). Complex 5a in a noncoordinating solvent such as CH2C12 or CHCl3 suffered spontaneous decarbonylation to form first cis-[Pt(COPh)(CO)(PPh3)2l(BF4) (3a) then the thermodynamically stable isomer trans-[Pt(COPh)(CO)(PPh3)2](BF4) (3b). Crystallization of complex 3b under ambient conditions resulted in an aqua benzoyl complex trans-[Pt(COPh)(OH2)(PPh3)2](BF4) (7). The replacement of the H2O ligand in complex 7 by CO was done simply by bubbling CO into the solution of 7. The single crystal structures of 5b and 7 have been determined by X-ray diffraction. The distances of the Pt-O bonds in 5a, 5b, and 7 support that the aqua ligand is a weak donor in such cationic aquaorganoplatinum(lI) complexes, in agreement with their lability to the substitution reactions. 相似文献
12.
《Journal of organometallic chemistry》1986,315(2):255-268
The reactions of Pt(PPH3)4 and Pt(C2H4)(PPh3)2 with CH2ClI have been investigated. The product of the reaction of Pt(PPh3)4 with CH2ClI is the cationic ylide complex cis-[Pt(CH2PPh3)Cl(PPh3)2][I], whereas the reaction of Pt(C2H4)-(PPh3)2 gives the oxidative addition product Pt(CH2Cl)I(PPh3)2. Reaction of cis- or trans-Pt(CH2Cl)I(PPh3)2] with PPh3 gives the complex cis-[Pt(CH2PPh3)-Cl(PPh3)2][I]. The structures of the complexes cis-[Pt(CH2PPh3X(PPh3)2][I] (where X = Cl or I) have been determined by X-ray crystallography. Both complexes crystalize in the monoclinic space group P21/n. For X = Cl a 1388.6(7), b 2026.7(10), c 1823.9(9) pm, β 96.51(2)° and R converged to 0.075 for 3542 observed reflections; structural parameters Pt-Cl 240(1), Pt-C(3) 212(2), Pt-P(2) (trans to Cl) 235(1) and Pt-P(1) (trans to CH2PPh3) 233(1) pm; Cl-Pt-C(3) 86.9(5), C(3)-Pt-P(2) 91.8(5), P(2)-Pt-P(1) 97.0(2) and P(1)-Pt-Cl 85.1(2)°. For X = I, a 1379.4(7), b 2044.4(10), c 1840.0(9) pm, β 96.09(2)° and R converged to 0.071 for 4333 observed reflections; structural parameters Pt-I 266(1), Pt-C(3) 212(2), Pt-P(2) (trans to I) 226(1) and Pt-P(1) (trans to CH2PPh3 233(1) pm; I-Pt-C(3) 87.2(5), C(3)-Pt-P(2) 91.5(5), P(2)-Pt-P(1) 96.5(2) and P(1)-Pt-I 85.6(1)°. Some other complexes of the type cis-[Pt(CH2PPh3)X(PPh3)2]Y are also described. 相似文献
13.
Summary Reactions of cinnamonitrile (trans-PhCH=CHCN) with [M(ClO4)(CO)(PPh3)2] (M=Rh or Ir) produce hydrogenation oftrans-PhCH=CHCN to PhCH2CH2CN at 100°C under 3 atm of hydrogen. 相似文献
14.
Os(η2-CH2O)(CO)2(PPh3)2 reacts with CSe2 to form a metallacycle O]Se)(CO)2(PPh3)2. This compound breaks down to Os(η2-CH2Se)(CO)2(PPh3)2 with probable loss of COSe. An alternative route to Os(η2-CH2Se)(CO)2(PPh3)2 and also Os(η2-CH2Te)(CO)2(PPh3)2 is through reaction of Os(CH2I)I(CO)2(PPh3)2 with SeH? and TeH?, respectively. HCl with Os(η2-CH2E)(CO)2(PPh3)2 (E = Se or Te) gives OsCl(EMe)(CO)2(PPh3)2 while methyl iodide gives [Os(η2-CH2EMe)(CO)2 - (PPh3)2] I. BH4? reacts with these cations to cleave the CE bond and form Os(CH3)(EMe)(CO)2(PPh3)2. 相似文献
15.
《Journal of Coordination Chemistry》2012,65(1-4):57-66
Abstract Treatment of trans-[Mo(N2)2(dpe)(dpm)] (dpe = Ph2PCH2CH2PPh2, dpm = Ph2PCH2PPh2) or trans-[Mo(N2)2(dpe)(dpp)] (dpp = Ph2PCH2CH2CH2PPh2) with excess DMF in benzene at reflux under Ar resulted in the formation of trans-[Mo(CO)(DMF)(dpe)(dpm)] or trans-[Mo(CO)(DMF)(dpe)(dpp)]. X-ray structural analysis of trans-[Mo(CO)(DMF)(dpe)2] was performed using single crystals isolated as the minor product from the reaction mixture of trans-[Mo(N2)2(dpe)(dpp)] and DMF. Crystal data: C56H55O2NP4Mo, monoclinic, space group P21, a = 11.145(4), b = 23.425(5), c = 10.516(3) Å, β = 117.17(2)° V = 2442.6(13) Å3, D calcd = 1.35 g/cm3 for Z = 2. This disclosed the relatively long C O bond distance of the carbonyl ligand and the significantly short C=O bond length in the DMF ligand. When recrystallized from benzene/hexane under N2, trans-[Mo(CO)(DMF)(dpe)(dpm)] was converted into trans-[Mo(CO)(N2)(dpe)(dpm)]. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(10):1553-1567
Synthetic procedures are described that allow access to cis-[Mo2O5(cdhp)2]2?, cis-[W2O5(Hcdhp)2], trans-[OsO2(cdhp)2]2?, trans-[UO2(Hcdhp)2], [ReO(PPh3)(Hcdhp)2]X (X =?Cl, I), [ReO2(cdhp)2]?, [M(PPh3)2(cdhp)], [M(bpy)(cdhp)] (M(II) =?Pd, Pt), [Ru(YPh3)2(Hcdhp)2] (Y =?P, As), [Rh(Hcdhp)2Cl(H2O)], [Rh(PPh3)2(Hcdhp)2]ClO4 and [Ir(bpy)(cdhp)Cl2], where Hcdhp, cdhp are the deprotonated monoanion of 5-chloro-3-hydroxypyrid-2-one and dianion of 5-chloro-2,3-dihydroxypyridine, respectively. These complexes were characterized by their Raman, IR, 1H NMR, electronic and mass spectra, conductivity, magnetic and thermal measurements. H2cdhp, cis-K2[Mo2O5(cdhp)2], [Pd(bpy)(cdhp)] display a significant antineoplastic activity against Ehrlich ascites tumor cells (EAC). 相似文献
17.
Summary The rhodium(I) carbonyl compounds [Rh(CO)L22] [BF4]. 1/2CH2Clnn2 (L = PPh2 or AsPh3) react with the nucleophiles OMe−, RCOO− (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L2] (1)–(2) and [Rh(OOCR)(CO)L2] (7)–(10), respectively. Addition of [Rh(CO)2(PPh3)2]-[BF 4] to OMe− under nitrogen produces [Rh(COOMe)-(CO) (PPh3)2]-MeOH (3), whilst reactions of [Rh(CO)-(PPh3)2] [BF4]·1/2CH2Cl2 and [Rh(CO)2(PPh3)2] [BF4] with OR- (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO)2(PPh3)2] (4)–(6). The products have been characterised by i.r., 1H, 31P, 13Cn.m.r. spectroscopy and elemental analysis. 相似文献
18.
L. F. Krylova L. M. Kovtunova G. V. Romanenko L. A. Sheludyakova 《Russian Journal of Coordination Chemistry》2012,38(5):363-372
Stereoisomeric Pt(IV) complexes with threonine (ThrH = HOCH(CH3)CH(NH2)COOH, ??-amino-??-hydroxybutyric acid) were obtained. In the complexes trans-[Pt(S-ThrH)2Cl4] and trans-[Pt(R-ThrH)(S-ThrH)Cl4], the ThrH molecules act as monodentate ligands coordinated through the NH2 group. In the complexes cis- and trans-[Pt(S-Thr)2Cl2] and trans-[Pt(R-Thr)(S-Thr)Cl2], the deprotonated ligands are coordinated in a bidentate fashion through the NH2 and COO?-groups (R,S is the absolute configuration of the asymmetric carbon atom). All the complexes were identified using elemental analysis, IR spectroscopy, and 195Pt, 13C, and 1H NMR spectroscopy. The complexes trans-[Pt(S-ThrH)2Cl4] · 3H2O and cis-[Pt(S-Thr)2Cl2] · 2H2O were additionally characterized by X-ray diffraction. 相似文献
19.
《Journal of organometallic chemistry》1990,395(2):C35-C38
The reactions of K[HB(pz)3] (pz = pyrazol-1-yl) with the coordinatively unsaturated σ-vinyl complexes [Ru(CRCHR)Cl(CO)(PPh3)2] (R = H, Me, C6H5) proceed with loss of a chloride and a phosphine ligand to provide the compounds [Ru(CRCHR)(CO)(PPh3){HB(pz)3}] in high yield. Similar treatment of the complex [Ru(C6H4Me-4)Cl(CO)(PPh3)2] leads to the related σ-aryl derivative [Ru(C6H4Me-4)(CO)(PPh3){HB(pz)3}] whilst the complex [RuClH(CO)(PPh3)3] treated successively with diphenylbutadiyne and K[HB(pz)3] provides the unusual derivative [Ru{C(CCPh)CHPh}(CO)(PPh3){HB(pz)3}]. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(3-4):349-357
Abstract Reactions of HBr with trans-[W(N2)2(dppe)PPh2Me)2] (1) (dppe = Ph2CH2CH2PPh2) result in protonation of coordinated N2 but no formation of ammonia or hydrazine. The tungsten-containing product depends upon the reaction conditions: (i) in MeOH, the product formed is [WBr(NNH2) (dppe)(PPh2Me)2]HBr2 (2) which converts to the hydride, [WBr2(H)(NNH2(dppe)(PPh2Me)](Br(3), with loss of phosphine in THF or CH2Cl2, (ii) in THF or CH2Cl2, the hydride (3) is formed directly. Reaction of 2 with Na2CO3 in MeOH results in the loss of HBr and the formation of the diazenido complex [WBr(NNH)(dppe)(PPh2Me)2] which reacts further with Na2CO3 in benzene under N2 to lose HBr and form a mixture of 1 and trans-[W(N2)(dppe)2]. The reaction of 1 with aqueous HF forms [WF(NNH2)(dppe)(PPh2Me)2]BF4. The X-ray photoelectron spectra of trans-[M(N2)2 (dppe)2], [MBr(NNH2)(dppe)2Br (M = Mo, W), [WCl(NNH2)(dppe)2]Cl, [WCl(N)(dppe)2]Cl and [WCl(NH) (dppe)2] are reported. In all of these complexes, nitrogen is in a highly reduced form. 相似文献