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1.
A high-yield synthesis of [IrCl(cod)]2 (cod = 1,5-cyclooctadiene) is described. The 1H and 13C NMR spectra of a number of complexes [IrCl(cod)L] are interpreted in terms of a trans-effect series Cl? < sym-collidine < 2-picoline < PCy3 < P-i-Pr3 < Pet3 ~ AsPh3 < PMe2Ph < PMePh2 < PPh2 <P(MeO)Ph2 < PClPh2 < P(OPh)3 < PCl2Ph. Some ligand exchange reactions of [IrCl(cod)L] are discussed. A number of complexes of the type [Ir(cod)Ln]PF6 (L = a variety of amines (n = 2) and phosphines (n = 2 or 3)) are described. Exchange reactions of the sort: [Ir(cod)(PR3)2]PF6 + [Ir(cod)(py)2]PF6 ? [Ir(cod)(PR3)Py]PF6 are reported in which, surprisingly, the isolable mixed ligand complexes are the only detectable species at equilibrium (py = pyridine). 相似文献
2.
Novel complexes [Pt(C5H6O2)L2] (IVa, L = PPh3; IVb, L = PMePh2, IVc, L = PMe2Ph) were prepared by the reactions of [Pt(acac)2] with tertiary phosphines either at elevated temperature (when L = PPh3) or at room temperature (L = PMePh2 and PMe2Ph), whereas AsPh3 yielded [Pt(acac)(γ-acac)AsPh3] (Id) by the reaction with [Pt(acac)2] even under rigorous conditions. Complexes IV were characterized on the basis of their IR and NMR spectra, elemental analyses and chemical reactions, and a structure which possesses a chelate type “acetylacetonato” ligand involving π-oxoallyl bonding is proposed. 相似文献
3.
Michael P. Brown Susan J. Franklin Richard J. Puddephatt Mary A. Thomson Kenneth R. Seddon 《Journal of organometallic chemistry》1979,178(1):281-290
Reaction of [Pt2Cl2(μ-dppm)2] with ligands, L, in the presence of [PF6- gave stable cationic diplatinum(I) complexes [Pt2L2(μ-dppm)2][PF6]2 where L = PMe2Ph, PMePh2, PPh3, NH3, C5H5N. Reaction of [Pt2(NH3)2(μ-dppm)2][PF6]2 with CO gave [Pt2(CO)2(μ-dppm)2][PF6]2 and an unsymmetrical complex [Pt2(CO)(C5H5N)(μ-dppm)2][PF6]2 was also prepared. The compounds were characterized by vibrational and 1H and 31P NMR spectroscopy and the presence of direct platinumplatinum bonds is indicated. 相似文献
4.
Summary The preparation, structural study and chemical behaviour of new cationic, monoanionic and dianionic tetracoordinate nickel(I) complexes of the types: [NiL4][BPh4] (L=PPh3, AsPh3 or SbPh3), [PR4][NiX2L2] (X=Cl, Br or I; L=PPh3, AsPh3 or SbPh3 and [PR4]+=PPh4, Ph3PCH2Ph or Ph3PEt) and [PR4]2[NiX3L] (X=Cl, Br or I; L=PPh3 and [PR4]+=PPh4 or PPh3CH2Ph) are described. 相似文献
5.
ortho-Substituted aryliridium(I) complexes of the type [Ir(RnC6H5-n)(CO)L2] (RnC6H5-n = 2-EtC6H4; 2,6-Et2C6H3; L = PPh3 PMePh2) have been prepared from [IrCl(CO)L2] and the corresponding aryllithiums. With the exception of trans-[Ir(2-EtC6H4)(CO)(PPh3)2] these compounds show cis, trans isomerism. After separation, the isomers have been studied by NMR (1H, 31P), IR, and UV-VIS spectroscopy. ab]Durch Umsetzung von [IrCl(CO)L2] (L = PPh3, PMePh2) mit den entsprechenden Lithiumarylen wurden ortho-substituierte Aryliridium(I)-Komplexe des Typs [Ir(Rn C6H5-n)(CO)L2] (RnC6H5?n = 2-EtC6H4; 2,6-Et2C6H3; 2-Et-6-MeC6H3) dargestellt. Mit Ausnahme von trans-[Ir(2-EtC6H4)(CO)(PPh3)2] zeigen diese Verbindungen die Erscheinung der cis,trans-Isomerie. Die Isomere wurden getrennt und mit Hilfe NMR- (1H, 31P), IR- und UV/VIS-spektroskopischer Methoden untersucht. 相似文献
6.
The mechanism of but-1-ene, pent-1-ene and 3-methylbut-1-ene isomerization catalysed with trans-[PtH(SnX3)L2] (I, L = PPh3, PMePh2, PEt3, PPr3; X = Cl, Br) have been studied. Stoichiometric reactions of I with the alkenes proceed even at ?90°C giving cis-[Pt(alkyI-1) (SnX3) L2] (II). The equilibrium amounts of II are dependent on the nature of the phosphines, halogens and alkenes. The isomerization rates, determined at +20°C, change in parallel with the relative stabilities of II as a function of phosphine (PMePh2 > PPh3 > PAlk3) and halogen (Br > Cl), and decrease with methyl substitution at γ- and δ- carbons of the alkenes. 2-Substituted alk-1-enes undergo no isomerization in the reactions under investigation. When L is PPh3 or PMePh2, the main platinum-containing species in the course of the isomerization are trans-[Pt(alkyl-1) (SnX3)L2], appearing as a result of cis-trans isomerization of II. The conversion of I, L = PAlk3 into related trans-alkyl complexes, and oxidation of I, proceed more slowly than the isomerization of alkenes. The ratio of cis- to trans-alk-2-enes is dependent on the size of L and is a maximum for L = PPh3. 相似文献
7.
《Journal of organometallic chemistry》2003,665(1-2):15-22
The keto-functionalised N-pyrrolyl phosphine ligand PPh2NC4H3{C(O)CH3-2} L1 reacts with [MoCl(CO)3(η5-C5R5)] (R=H, Me) to give [MoCl(CO)2(L1-κ1P)(η5-C5R5)] (R=H 1a; Me 1b). The phosphine ligands PPh2CH2C(O)Ph (L2) and PPh2CH2C(O)NPh2 (L3) react with [MoCl(CO)3(η5-C5R5)] in an analogous manner to give the compounds [MoCl(CO)2(L-κ1P)(η5-C5R5)] (L=L2, R=H 2a, Me 2b; L=L3, R=H 3a, Me 3b). Compounds 1–3 react with AgBF4 to give [Mo(CO)2(L-κ2P,O)(η5-C5R5)]BF4 (L=L1, R=H 4a, Me 4b; L=L2, R=H 5a, Me 5b; L=L3, R=H 6a, Me 6b) following displacement of chloride. The X-ray crystal structure of 4a revealed a lengthening of both Mo–P and CO bonds on co-ordination of the keto group. The lability of the co-ordinated keto or amido group has been assessed by addition of a range of phosphines to compounds 4–6. Compound 4a reacts with PMe3, PMe2Ph and PMePh2 to give [Mo(CO)2(L1-κ1P)(L)(η5-C5H5)]BF4 (L=PMe3 7a; PMe2Ph 7b; PMePh2 7c) but does not react with PPh3, 5a reacts with PMe2Ph, PMePh2 and PPh3 to give [Mo(CO)2(L2-κ1P)(L)(η5-C5H5)]BF4 (L=PMe2Ph 8b; PMePh2 8c; PPh3 8d), and 6a reacts with PMe3, PMe2Ph, PMePh2 and PPh3 to give [Mo(CO)2(L3-κ1P)(L)(η5-C5H5)]BF4 (L=PMe3 10a; PMe2Ph 10b; PMePh2 10c; PPh3 10d). No reaction was observed for the pentamethylcyclopentadienyl compounds 4b–6b with PMe3, PMe2Ph, PMePh2 or PPh3. These results are consistent with the displacement of the co-ordinated oxygen atom being influenced by the steric properties of the P,O-ligand, with PPh3 displacing the keto group from L2 but not from the bulkier L1. In the reaction of [Mo(CO)2(L2-κ2P,O)(η5-C5H5)]BF4 (5a) with PMe3 the phosphine does not displace the keto group, instead it acts as a base, with the only observed molybdenum-containing product being the enolate compound [Mo(CO)2{PPh2CHC(O)Ph-κ2P,O}(η5-C5H5)] 9. Compound 9 can also be formed from the reaction of 2a with BuLi or NEt3, and a single crystal X-ray analysis has confirmed the enolate structure. 相似文献
8.
《Polyhedron》1999,18(8-9):1141-1145
Exchange reactions of trans-[PdXPh(SbPh3)2] (1) (X=Cl or Br) with ligands L in refluxing dichloromethane give the palladium phenyl complexes [PdXPhL2] (X=Cl, L=PPh3, AsPh3, L2=2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (dmbipy), 1,10-phenanthroline (phen); X=Br, L=PPh3, L2=bipy). Treatment of the complexes with bis(diphenylphosphino)methane (dppm) in refluxing dichloromethane gives [PdXPh(dppm]2. These complexes have been characterised by microanalysis, IR and 1H NMR spectroscopic data together with single crystal X-ray determinations of the phenyl palladium complexes, trans-[PdClPh(PPh3)2], [PdClPh(bipy)], [PdClPh(dppm)]2, and [PdBrPh(dppm)]2. 相似文献
9.
A series of gold(III) cations of the type cis-[CH3)2AuL2]+ X? where L Ph3, PMePh2, PMe2Ph, PMe3, AsPh3, AsPh3, SbPh3, H2NCH2CH2NH2, Ph2PCH2CH2-PPh2, Ph2AsCH2CH2AsPh2, and o-C6H4(AsMe2)2 and X BF4?, PF6?, ClO4?, and F3CSO3? has been prepared. In addition, the cis complexes [(CH3)(CD3)-Au(PPh3)2]F3CSO3, [(C2H5)2Au(PPh3)2]F3CSO and [(n-C4H9)2Au(PPh3)2]F3-CSO3 have been synthesized. All have been characterized by PMR, Raman and infrared spectroscopy. These [R2AuL2]X compounds yield only ethane, butane, or octane via reductive elimination, and no disproportionation is observed. The alkane eliminations have been studied in CHCl3, CH3Cl2, and CH3COCH3 solution as a function of temperature, concentration of the complex, and concentration of added ligand L. Elimination is fastest when L is bulky (PPh3 > PMePh2 > PMe2Ph > PMe3), decreases in the sequence SbPh3 > AsPh3 > PPh3, is slow with chelating ligands, is inhibited by excess ligand, and there is small anion effect as X is varied. As R is varied, the rate of elimination decreases Bu ? Et > Me. An intramolecular dissociative mechanism is proposed which involves rapid elimination of alkane from an electron deficient dialkylgold(III) complex with nonequivalent gold—carbon bonds and produces the corresponding [AuL2]X complex. 相似文献
10.
The complexes trans-MCl2(PMe3)4 (M = Ru, Os) react with CO and P(OMe)3 to give the mono- and disubstituted derivatives trans,mer-MCl2(PMe3)3L (L = CO, P(OMe)3) and all-trans-MCl2(PMe3)2[P(OMe)3]2, respectively. On reaction of trans-RuCl2[P(OMe)3]4 with CO and PMe3, the compounds trans,mer-RuCl2[P(OMe)3]3(CO) and trans,cis,cis-RuCl2(PMe3)2[P(OMe)3]2 are synthesized. The reduction of MCl2(PMe3)2[P(OMe)3]2 with Na/Hg in benzene or toluene via {M(PMe3)2[P(OMe)3]2} as an intermediate leads to subsequent intermolecular addition of the arene and to the aryl(hydrido)metal complexes cis,trans,cis-MH(C6H5)(PMe3)2[P(OMe)3]2 (M = Ru, Os) and MH(C6H4CH3)(PMe3)2[P(OMe)3)2 (M = Os). For M = Ru, in the presence of P(OMe)3, the ruthenium(0) compound Ru(PMe3)2(P(OMe)3]3 is formed. The hydrido(phenyl) complexes react with equimolar amounts of Br2 or I2 by elimination of benzene to produce the dihalogenometal compounds cis,trans,cis-MX2(PMe3)2[P(OMe)3]2. The reaction of trans-RuCl2(PMe3)4 with Na/Hg in the presence of PPh3 leads to the ortho-metallated complex fac-RuH(η2-C6H4PPh2)(PMe3)3, which reacts with CH3I, CS2, COS and HCl to give the compounds mer-RuI(η2-C6H4PPh2)(PMe3)3, fac-Ru(SCHS)(η2-C6H4PPh2)(PMe3)3, fac-Ru(S2CO)(CO)(PMe3)3 and RuCl2(PMe3)3, respectively. The paramagnetic 17-electron complexes [MCl2(PMe3)nL4-n]PF6 are obtained on oxidation of MCl2(PMe3)nL4-n with AgPF6. Their UV spectra exhibit a characteristic CT band. [RuCl2(PMe3)4]PF6 and [OsCl2(PMe3)4]PF6 react with CO and P(OMe)3 by reduction to form the corresponding ruthenium(II) and osmium(II) compounds MCl2(PMe3)nL4-n. 相似文献
11.
《Journal of Coordination Chemistry》2012,65(15):1655-1665
The reactivity of mixed [organohydrazido(1-)][organohydrazido(2-)]molybdenum(VI) complexes [Mo(NHNRPh)(NNRPh)(acac)X2] {R?=?Ph, X?=?Br (1); R?=?Ph, X?=?I (2) and R?=?Me; X?=?I (3)} with tertiary phosphines as PPh3, PMePh2 and PMe2Ph are examined. The syntheses of [Mo(NNPh2)2Br2(PPh3)] (4), [Mo(NNPh2)2Br2(PMePh2)2] (5), [Mo(NNPh2)2Br2(PMe2Ph)2] (6), [Mo(NNPh2)2(acac)I(PPh3)] (7), [Mo(NNPh2)2(acac)(PMePh2)2]+I? (8) and [Mo(NNMePh)2(acac)(PMePh2)2]+I? (9) are reported. All complexes were characterized by elemental analysis, UV-visible, IR, 1H and 31P{H} NMR spectroscopy. 相似文献
12.
Marym Lashanizadehgan Mehdi Rashidi Janet E. Hux Richard J. Puddephatt Samson S.M. Ling 《Journal of organometallic chemistry》1984,269(3):317-322
Reaction of excess MeLi and MeI with [PtCl2SMe2)2] gives the first binuclear tetramethylplatinum(IV) complex [Pt2Me8(μ-SMe2)2]. The characterization of this complex, and its reactions with donor ligands to give cis-[PtMe4L2] (L2 = Ph2PCH2PPh2, Ph2PCH2CH2PPh2, 2,2′-bipyridyl, 1,10-phenanthroline or L = PMe2Ph, PMePh2) are described. 相似文献
13.
Summary The reduction of nickel(II) halides with NaBH4 in the presence of different ligands, L=PPh3, AsPh3, SbPh3, has been studied. With a molar ratio L/Ni=3, new complexes NiX(SbPh3)3, X=Cl, Br, I, were obtained. With a molar ratio L/Ni=2, dimeric species [NiXL2]2, X=Cl, Br, I; L=PPh3, AsPh3, SbPh3, were isolated. They are unstable and decompose easily in the solid and rapidly in solution, so that pure samples were only identified for X=Cl, L=PPh3, AsPh3, SbPh3; X=Br, L=PPh3 and X=I, L=PPh3. With a molar ratio L/Ni=1, complexes [NiXL]n (probably polymeric) were obtained. They are very unstable and pure samples could only be isolated when X=Cl, L=PPh3. Impure substances containing variable amounts of decomposition products were obtained in all the remaining cases. The chemical and structural behaviour of these complexes is discussed. 相似文献
14.
UV photolysis of [CpFeII(CO)3]+ PF66? (I) or [CpFeII(η6-toluene)]+ PF6?? (II) in CH3CN in the presence of 1 mole of a ligand L gives the new air sensitive, red complexes [CpFeII(NCCH3)2L]+PF6? (III, L = PPh3; IV; L = CO; VIII, L = cyclohexene; IX, L = dimethylthiophene) and the known air stable complex [CpFeII(PMe3)2(NCMe)]+ PF6? (V). The last product is also obtained by photolysis in the presence of 2 or 3 moles of PMe3. In the presence of dppe, the known complex [CpFeII (dppe)(NCCH3)]+ (XI) is obtained. Complex III reacts with CO under mild conditions to give the known complex [CpFe(NCCH3)(PPh3)CO]+ PF6? (X). UV photolysis of I in CH3CN in the presence of 1-phenyl-3,4-dimethylphosphole (P) gives [CpFeIIP3]+ PF6? (XII); UV photolysis of II in CH2Cl2 in the presence of 3 moles of PMe3 or I mole of tripod (CH3C(CH2Ph2)3) provides an easy synthesis of the known complexes [CpFeII(PMe3)3]+ PF6? (VII) or [CpFeIIη3-tripod]+ PF6t- (XIII). Since I and II are easily accessible from ferrocene, these photolytic syntheses provide access to a wide range of piano-stool cyclopentadienyliron(II) cations in a 2-step process from ferrocene. 相似文献
15.
A route to the stable hydrido-diene salts [(diene)RuHL3] PF6, (diene = cycloocta-l,5-diene, hexa-l,3-diene and buta-1,3-diene, L = PMe2 Ph; diene = cycloocta-l,5-diene, L = P(OMe)3, P(OCH2)3 CMe P(OMe)Ph2 and PMePh2) has been found and the structure of [RuH(C4H6)(PMe2Ph)3] PF6 has been determined by X-ray diffraction. 相似文献
16.
Jan Schiemann Erwin Weiss Fritz Näumann Dieter Rehder 《Journal of organometallic chemistry》1982,232(3):219-227
Numerous new complexes of the type V(CO)5n(NO)Ln, have been prepared either by nitrosylation of [V(CO)6nLn]?(n 2, 3) with NOX (X Cl, BF4) and [Co(NO)2Br]2, resp., or by reaction of L with “V(CO)5NO” generated in situ. The compounds comprise n 1: L PPh3, PMe2H, P(OMe)3 and Ph2PCH2?PPh2 (dppm); n 2: L22 2 PMe2H, 2 PMe3, 2 P(OMe)3, dppm, Ph2P(CH2)2?PPh2, Ph2P(CH2)3,PPh2, Me2P(CH2)2PMe2, Ph2As(CH2)2AsPh2, o?C6H4(AsMe2)2 (diars) and o?C6H4(AsPh2)PPh2; n 3: L3 1.5 diars and CH3C(CH2PPh2)3. IR (CO and NO stretching region) and 51V NMR spectra are discussed; for n 2 and 3, the positions of the arsine and phosphine ligands relative to NO are either cis for all the ligand functions (arsines) or cis/trans. 相似文献
17.
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
18.
The reaction of [Pt2X2(-Cl)2(PR3)2] with NaSpy or NaSepy gave complexes of the type [PtX(Epy)(PR3)]n (X=Cl or Ar; E=S or Se; PR3=PEt3, PMe2Ph, PMePh2 or PPh3; n=1 or 2) which were characterized by elemental analysis and by 1H, 31P{1H}, 195Pt{1H} n.m.r. spectroscopy. When X=Cl a dynamic equilibrium between [Pt2Cl2(-Spy)2(PR3)2] and [PtCl(k-S,N-Spy)(PR3)] species exists in CHCl3 solution. The aryl derivatives, X=Ar, exist exclusively as dimers (n=2) with predominantly SN bridging. The [Pt(Spy)2 (PPh3)2] complex, prepared by reacting [PtCl2 (PPh3)2] with NaSpy, dissociates in CHCl3 to [Pt(k-S,N-Spy) (Spy)(PPh3)] and PPh3 at room temperature. 相似文献
19.
Dipl.‐Chem. Inmaculada Mena Dr. E. A. Jaseer Dr. Miguel A. Casado Dr. Pilar García‐Orduña Prof. Fernando J. Lahoz Prof. Luis A. Oro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(18):5665-5675
The ready availability of rare parent amido d8 complexes of the type [{M(μ‐NH2)(cod)}2] (M=Rh ( 1 ), Ir ( 2 ); cod=1,5‐cyclooctadiene) through the direct use of gaseous ammonia has allowed the study of their reactivity. Both complexes 1 and 2 exchanged the di‐olefines by carbon monoxide to give the dinuclear tetracarbonyl derivatives [{M(μ‐NH2)(CO)2}2] (M=Rh or Ir). The diiridium(I) complex 2 reacted with chloroalkanes such as CH2Cl2 or CHCl3, giving the diiridium(II) products [(Cl)(cod)Ir(μ‐NH2)2Ir(cod)(R)] (R=CH2Cl or CHCl2) as a result of a two‐center oxidative addition and concomitant metal–metal bond formation. However, reaction with ClCH2CH2Cl afforded the symmetrical adduct [{Ir(μ‐NH2)(Cl)(cod)}2] upon release of ethylene. We found that the rhodium complex 1 exchanged the di‐olefines stepwise upon addition of selected phosphanes (PPh3, PMePh2, PMe2Ph) without splitting of the amido bridges, allowing the detection of mixed COD/phosphane dinuclear complexes [(cod)Rh(μ‐NH2)2Rh(PR3)2], and finally the isolation of the respective tetraphosphanes [{Rh(μ‐NH2)(PR3)2}2]. On the other hand, the iridium complex 2 reacted with PMe2Ph by splitting the amido bridges and leading to the very rare terminal amido complex [Ir(cod)(NH2)(PMePh2)2]. This compound was found to be very reactive towards traces of water, giving the more stable terminal hydroxo complex [Ir(cod)(OH)(PMePh2)2]. The heterocyclic carbene IPr (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) also split the amido bridges in complexes 1 and 2 , allowing in the case of iridium to characterize in situ the terminal amido complex [Ir(cod)(IPr)(NH2)]. However, when rhodium was involved, the known hydroxo complex [Rh(cod)(IPr)(OH)] was isolated as final product. On the other hand, we tested complexes 1 and 2 as catalysts in the transfer hydrogenation of acetophenone with iPrOH without the use of any base or in the presence of Cs2CO3, finding that the iridium complex 2 is more active than the rhodium analogue 1 . 相似文献
20.
Stephen M. Aucott Colin J. Burchell Alexandra M. Z. Slawin J. Derek Woollins 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4-5):903-906
The addition of dichloromethane solutions of carbon diselenide to liquid ammonia containing suspensions of platinum bis-phosphine dichlorides [PtCl2(PRX)n] (n = 2, (PRX) = PMe3, PMe2Ph, PMePh2, and PPh3, n = 1, (PRX) = dppm, dppe, dppp, dppf) gives, after evaporation of the ammonia and extraction of the reaction residues with dichloromethane, the appropriate platinum bis-phosphine triselenocarbonate complexes in reasonable yields (40–60%). 相似文献