How to turn the catalytic asymmetric hydroboration reaction of vinylarenes into a recyclable process

Optically pure rhodium(I) complexes [Rh(cod)(Lbond;L)]X (cod=cyclooctadiene; L-L= (R)-2,2'-bis(diphenylphosphino)1-1'-binaphthyl ((R)-BINAP), (S,S)-2,4-bis(diphenylphosphino)pentane ((S,S)-BDPP), 2-diphenylphosphino-1-(1'-isoquinolyl)naphthalene ((S)-QUINAP); X=BF(4), PF(6), SO(3)CF(3), BPh(4)) were immobilised onto smectite clays such as montmorillonite K-10 (MK-10) and bentonite (Na(+)-M). (19)F, (31)P and (11)B NMR experiments recorded in CDCl(3) during the impregnation process provided evidence that montmorillonite K-10 may immobilise ionic metal complexes throughout the cationic and anionic counterparts. However, when bentonite was used as the solid, only the cationic metal complex was immobilised through cationic exchange while the counteranion remained in solution. When we used these preformed catalytic systems in the hydroboration of prochiral vinylarenes, we obtained high activities and enantiomeric excess with (S)-1-(2-diphenylphosphino-1-naphthyl)isoquinoline-modified rhodium complexes. These activities and selectivities are competitive with the homogeneous counterparts. The significant features of this method are the simple separation and good retention of the active metal in the solid, which allows efficient recycling even on exposure to air.     

Asymmetric hydrogenation of prochiral olefins catalysed by furanoside thioether-phosphinite Rh(I) and Ir(I) complexes

Thioether-phosphinite ligands (P-SR, R = Ph, Pr(I) and Me) bearing substituents with different steric demands on the sulfur centre were tested in the rhodium- and iridium-catalysed asymmetric hydrogenation of prochiral olefins. High enantiomeric excesses (up to 96%) and good activities (TOF up to 860 mol product x (mol catalyst precursor x h)(-1)) were obtained for alpha-acylaminoacrylates derivatives. Our results show that enantiomeric excesses depended strongly on the steric properties of the substituent in the thioether moiety, the metal source and the substrate structure. A bulky group in the thioether moiety along with the metal Rh had a positive effect on enantioselectivity. Reaction of these chiral ligands with [M(cod)2]BF4(M = Ir, Rh; cod = 1,5-cyclooctadiene) yielded complexes [M(cod)(P-SR)]BF4, which were present in only one diastereomeric form having the sulfur substituent in a pseudoaxial disposition. The addition of H2 to iridium complexes gave the cis-dihydridoiridium(iii) complexes [IrH2(cod)(P-SR)]BF4. For complexes [IrH2(cod)(P-SPh)]BF4 and [IrH2(cod)(P-SMe)] only one isomer was present in solution. However, for the complex [IrH2(cod)(P-Si-Pr)]BF4, which contained the more hindered substituent on sulfur, two isomers were detected. In all cases there was a pseudoaxial disposition of the sulfur substituents.     

On the origin of regio- and stereoselectivity in the rhodium-catalyzed vinylarenes hydroboration reaction

We studied the hydroboration of vinylarenes using rhodium complexes bearing atropoisomeric ligands. For the first time, an NMR spectroscopy study of the styrene and catecholborane addition to the precursor of catalyst [Rh(COD)(L-L)]BF(4), where L-L = (R)-BINAP and (R)-QUINAP, showed evidence of the structure of intermediates involved in the catalytic cycle. On the basis of this evidence, and using DFT calculations and QM/MM strategies, we investigated the origin of regio- and stereoselectivity. We determined the structure and stability of the key intermediates for several ligands and substrates and found excellent agreement between the relative stability of the intermediates and the experimentally observed trends. Using model systems, we analyzed the role of the steric and electronic features of the ligands and the substrates in detail.     

Phenoxyl radicals: H-bonded and coordinated to Cu(II) and Zn(II)

Two pro-ligands ((R)LH) comprised of an o,p-di-tert-butyl-substituted phenol covalently bonded to a benzimidazole ((Bz)LH) or a 4,5-di-p-methoxyphenyl substituted imidazole ((PhOMe)LH), have been structurally characterised. Each possesses an intramolecular O-H[dot dot dot]N hydrogen bond between the phenolic O-H group and an imidazole nitrogen atom and (1)H NMR studies show that this bond is retained in solution. Each (R)LH undergoes an electrochemically reversible, one-electron, oxidation to form the [(R)LH] (+) radical cation that is considered to be stabilised by an intramolecular O...H-N hydrogen bond. The (R)LH pro-ligands react with M(BF(4))(2).H(2)O (M = Cu or Zn) in the presence of Et(3)N to form the corresponding [M((R)L)(2)] compound. [Cu((Bz)L)(2)] (), [Cu((PhOMe)L)(2)] (), [Zn((Bz)L)(2)] and [Zn((PhOMe)L)(2)] have been isolated and the structures of .4MeCN, .2MeOH, .2MeCN and .2MeCN determined by X-ray crystallography. In each compound the metal possesses an N(2)O(2)-coordination sphere: in .4MeCN and .2MeOH the {CuN(2)O(2)} centre has a distorted square planar geometry; in .2MeCN and .2MeCN the {ZnN(2)O(2)} centre has a distorted tetrahedral geometry. The X-band EPR spectra of both and , in CH(2)Cl(2)-DMF (9 : 1) solution at 77 K, are consistent with the presence of a Cu(ii) complex having the structure identified by X-ray crystallography. Electrochemical studies have shown that each undergo two, one-electron, oxidations; the potentials of these processes and the UV/vis and EPR properties of the products indicate that each oxidation is ligand-based. The first oxidation produces [M(II)((R)L)((R)L )](+), comprising a M(ii) centre bound to a phenoxide ((R)L) and a phenoxyl radical ((R)L ) ligand; these cations have been generated electrochemically and, for R = PhOMe, chemically by oxidation with Ag[BF(4)]. The second oxidation produces [M(II)((R)L )(2)](2+). The information obtained from these investigations shows that a suitable pro-ligand design allows a relatively inert phenoxyl radical to be generated, stabilised by either a hydrogen bond, as in [(R)LH] (+) (R = Bz or PhOMe), or by coordination to a metal, as in [M(II)((R)L)((R)L )](+) (M = Cu or Zn; R = Bz or PhOMe). Coordination to a metal is more effective than hydrogen bonding in stabilising a phenoxyl radical and Cu(ii) is slightly more effective than Zn(II) in this respect.     

Early-late heterobimetallic alkoxides as model systems for late-transition-metal catalysts supported on titania

Titanium complexes with chelating alkoxide ligands [TiCp*(O(2)Bz)(OBzOH)] (1) and [TiCp*(Me)((OCH(2))(2)Py)] (2) were synthesised by reaction of [TiCp*Me(3)] (Cp*=eta(5)-C(5)Me(5)) with 2-hydroxybenzyl alcohol ((HO)(2)Bz) and 2,6-pyridinedimethanol ((HOCH(2))(2)Py), respectively. Complex 1 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) to yield the early-late heterobimetallic complexes [TiCp*(O(2)Bz)(2)M(cod)] [M=Rh (3), Ir (4)]. Carbon monoxide readily replaces the COD ligand in 3 to give the rhodium dicarbonyl derivative [TiCp*(O(2)Bz)(2)Rh(CO)(2)] (5). Compound 2 reacts with [(M(mu-OH)(cod))(2)] (M=Rh, Ir) with protonolysis of a Tibond;Me bond to give [TiCp*((OCH(2))(2)Py)(mu-O)M(cod)] [M=Rh (6), Ir (7)]. The molecular structures of complexes 3, 5 and 7 were established by single-crystal X-ray diffraction studies.     

A new route to achiral and chiral 1,2-bis(phosphino)ethanes, 1-arsino-2-phosphinoethanes, and 1,3-bis(phosphino)propanes and the molecular structure and catalytic activity of some rhodium(I) complexes derived thereof

A series of unsymmetrical 1,2-bis(phosphino)ethanes R(2)PCH(2)CH(2)PR'(2) and 1-arsino-2-phosphinoethanes R(2)AsCH(2)CH(2)PR'(2) mainly with bulky substituents R and R' were prepared from the cyclic sulfate by stepwise cleavage of the carbon-oxygen bonds by LiPR(2) and LiPR'(2) or LiAsR(2) and LiPR'(2), respectively. Analogously, racemic mixtures of R(2)PCH(2)CH(Me)PPh(2)(R =iPr, Cy ) as well as the enantiomers (R)-, (R)- and (R)-tBu(2)PCH(2)CH(Me)PPh(2)(R)- were obtained from the corresponding unsymmetrical cyclic sulfates and (S)-. On a similar route, the racemates of the 1,3-bis(phosphino)propanes R(2)PCH(2)CH(2)CH(Me)PPh(2)(R =iPr, tBu ), optically pure (R)- and (S,S)-iPr(2)PCH(Me)CH(2)CH(Me)PPh(2)(S,S)- were prepared. The reaction of [[RhCl([small eta](4)-C(8)H(12))](2)] with chelating ligands L-L, where L-L is R(2)PCH(2)P(men)(2)(R =iPr, Ph; men =(1S,2R,5S)-menthyl), Cy(2)AsCH(2)P(men)(2), or (R)-, (R)-, (R)-, (R)- and (S,S)-, in the presence of AgPF(6), gave the complexes [Rh(eta(4)-C(8)H(12))(L-L)]PF(6) which were used as pre-catalysts in the hydrogenation of the methyl ester of alpha-acetamidocinnamic acid (ACM). Depending on L-L, the solvent, the temperature and the pressure of H(2), optical yields of up to 69% ee were achieved. For two of the rhodium complexes, and, the molecular structures were determined by X-ray crystallography.     

Stepwise Construction of Polynuclear Complexes of Rhodium and Iridium Assisted by Benzimidazole-2-thiol. NMR and X-ray Diffraction Studies

Reactions of [M(2)(&mgr;-Cl)(2)(cod)(2)] (cod = 1,5-cyclooctadiene, M = Rh, Ir) with benzimidazole-2-thiol (H(2)Bzimt) afford the mononuclear complexes [MCl(H(2)Bzimt)(cod)] (M = Rh (1), Ir (2)) for which a S-coordination of the ligand is proposed based on their spectroscopic data. The dinuclear complexes [M(2)(&mgr;-HBzimt)(2)(cod)(2)] (M = Rh (3), Ir (4)) are isolated from the reaction of [M(acac)(cod)] and benzimidazole-2-thiol. They contain the monodeprotonated ligand (HBzimt(-)) bridging the two metals in a &mgr;(2)-(1kappaN,2kappaS) coordination mode and in a relative cis,cis-HT arrangement. Complexes 3 and 4 react with the appropriate species [M(cod)(Me(2)CO)(2)](+) to afford the trinuclear cationic aggregates [M(3)(&mgr;-HBzimt)(2)(cod)(3)](+) (M = Rh (5), Ir (6)) and with the [M'(2)(&mgr;-OMe)(2)(cod)(2)] compounds to give the homo- and heterotetranuclear complexes [MM'(&mgr;-Bzimt)(cod)(2)](2) (M = M' = Rh (7), Ir (8); M = Ir, M' = Rh (9)) containing the dideprotonated ligand (Bzimt(2)(-)). The trinuclear neutral complexes [M(3)(&mgr;-Bzimt)(&mgr;-HBzimt)(cod)(3)] are intermediates detected in the synthesis of the tetranuclear complexes. Protonation of 9 with HBF(4) gives the unsymmetrical complex [Ir(2)Rh(&mgr;-HBzimt)(2)(cod)(3)]BF(4) (10). This reaction involves the protonation of the bridging ligands followed by the removal of one "Rh(cod)" moiety to give a single isomer. The molecular structure of [Rh(2)(&mgr;-Bzimt)(cod)(2)](2) (7) has been determined by X-ray diffraction methods. Crystals are monoclinic, space group P2(1)/n, a = 20.173(5) ?, b = 42.076(8) ?, c = 10.983(3) ?, beta = 93.32(2) degrees, Z = 8, 7145 reflections, R = 0.0622, and R(w) = 0.0779. The complete assignment of the resonances of the (1)H NMR spectra of the complexes 3, 4, and 7-9 was carried out by selective decoupling, NOE, and H,H-COSY experiments. The differences in the chemical shifts of the olefinic protons are discussed on the basis of steric and magnetic anisotropy effects.     

Iridium-imine and -amine complexes relevant to the (S)-metolachlor process: structures, exchange kinetics, and C-H activation by Iri causing racemization

Iridium complexes of DMA-imine [2,6-dimethylphenyl-1'-methyl-2'-methoxyethylimine, 1 a) and (R)-DMA-amine [(1'R)-2,6-dimethylphenyl-1'-methyl-2'-methoxyethylamine, 2 a] that are relevant to the catalytic imine hydrogenation step of the Syngenta (S)-Metolachlor process were synthesized: metathetical exchange of [Ir2Cl2(cod)2] (cod=1,5-cyclooctadiene) with [Ag(1 a)2]BF4 and [Ag((R)-2 a)2]BF4 afforded [Ir(cod)(kappa2- -1 a)]BF4 (11) and [Ir(cod)(kappa2-(R)-2 a)]BF4 ((R)-19)), respectively. These complexes were then used in stopped-flow experiments to study the displacement of amine 2 a from complex 19 by imine 1 a to form the imine complex 11, thus modeling the product/substrate exchange step in the catalytic cycle. The data suggest a two-step associative mechanism characterized by k1=(2.6+/-0.3) x 10(2) M(-1) s(-1) and k2=(4.3+/-0.6) x 10(-2) s(-1) with the respective activation energies EA1=(7.5+/-0.6) kJ mol(-1) and EA2=(37+/-3) kJ mol(-1). Furthermore, complex 11 reacted with H2O to afford the hydrolysis product [Ir(cod)(eta(6-)-2,6-dimethylaniline)]BF4 (12), and with I2 to liberate quantitatively the DMA-iminium salt 14. On the other hand, the chiral amine complex (R)-19 formed the optically inactive eta6-bound compound [Ir(cod)(eta6-rac-2 a)]BF4 (rac-18) upon dissolution in THF at room temperature, presumably via intramolecular C-H activation. This racemization was found to be a two-step event with k'1=9.0 x 10(-4) s(-1) and k2=2.89 x 10(-5) s(-1), featuring an optically active intermediate prior to sp3 C-H activation. Compounds 11, 12, rac-18, and (R)-19 were structurally characterized by single-crystal X-ray analyses.     

Synthesis, structural characterization, and ligand replacement reactions of gem-dithiolato-bridged rhodium and iridium complexes

The reaction of gem-dithiol compounds R 2C(SH) 2 (R = Bn (benzyl), (i) Pr; R 2 = -(CH 2) 4-) with dinuclear rhodium or iridium complexes containing basic ligands such as [M(mu-OH)(cod)] 2 and [M(mu-OMe)(cod)] 2, or the mononuclear [M(acac)(cod)] (M = Rh, Ir, cod = 1,5-cyclooctadiene) in the presence of a external base, afforded the dinuclear complexes [M 2(mu-S 2CR 2)(cod) 2] ( 1- 4). The monodeprotonation of 1,1-dimercaptocyclopentane gave the mononuclear complex [Rh(HS 2Cptn)(cod)] ( 5) that is a precursor for the dinuclear compound [Rh 2(mu-S 2Cptn)(cod) 2] ( 6). Carbonylation of the diolefin compounds gave the complexes [Rh 2(mu-S 2CR 2)(CO) 4] ( 7- 9), which reacted with P-donor ligands to stereoselectively produce the trans isomer of the disubstituted complexes [Rh 2(mu-S 2CR 2)(CO) 2(PR' 3) 2] (R' = Ph, Cy (cyclohexyl)) ( 10- 13) and [Rh 2(mu-S 2CBn 2)(CO) 2{P(OR') 3} 2] (R' = Me, Ph) ( 14- 15). The substitution process in [Rh 2(mu-S 2CBn 2)(CO) 4] ( 7) by P(OMe) 3 has been studied by spectroscopic means and the full series of substituted complexes [Rh 2(mu-S 2CBn 2)(CO) 4- n {P(OR) 3} n ] ( n = 1, 4) has been identified in solution. The cis complex [Rh 2(mu-S 2CBn 2)(CO) 2(mu-dppb)] ( 16) was obtained by reaction of 7 with the diphosphine dppb (1,4-bis(diphenylphosphino)butane). The molecular structures of the diolefinic dinuclear complexes [Rh 2(mu-S 2CR 2)(cod) 2] (R = Bn ( 1), (i) Pr ( 2); R 2 = -(CH 2) 4- ( 6)) and that of the cis complex 16 have been studied by X-ray diffraction.     

TTF salts of optically pure cobalt pyridine amidates; detection of soluble assemblies with stoichiometry corresponding to the solid state

Optically pure anionic complexes of pyridinecarboxamide ligands, N(2),N(6)-bis((R)-α-methylbenzyl)pyridine-2, 6-dicarboxamide H(2)(R,R-L(1)) and N(2),N(6)-bis((S)-1-methoxypropan-2-yl)pyridine-2, 6-dicarboxamide H(2)(S,S-L(2)) have been synthesised and fully characterised. The complexes: (18-crown-6)K[Co(III)(R,R-L(1))(2)], (18-crown-6)K[Fe(III)(R,R-L(1))(2)] and K[Co(III)(S,S-L(2))(2)]·3H(2)O show interesting extended structures from 0D discrete units through 1D zigzag chains to 2D honeycomb layers. The complex anions were used in the synthesis of radical cation salts with tetrathiafulvalene (TTF). The salts (TTF)[Co(III)(R,R-L(1))(2)] and (TTF)[Co(III)(S,S-L(2))(2)]·EtOAc were characterised by single crystal X-ray diffraction and conductivity measurements. Both compounds comprise mono-oxidised TTF molecules and exhibit similar layered structures with no direct TTF stacking but in which phenyl substituents from the complex anion or co-crystallised ethyl acetate alternate with TTF(+) units. Solution spectroscopic and cyclic voltammetric evidence points to the formation of soluble assemblies between TTF(+) and the counterion which correspond to the stoichiometry observed by crystallography and other methods in the solid state.     

Chiral iridium [corrected] xyliphos complexes for the catalytic imine hydrogenation leading to the metolachlor herbicide: isolation of catalyst-substrate adducts

Iridium complexes relevant to the catalytic enantioselective hydrogenation of 2-methyl-6-ethylphenyl-1'-methyl-2'-methoxyethylimine (MEA-imine, 1) in the Syngenta Metolachlor (3) process were prepared and characterized. Reaction of the diphosphane (S)-1-[(R)-2-(diphenylphosphanyl)ferrocenyl]ethyldi(3,5-xylyl)phosphane ((S)-(R)-Xyliphos, (S)-(R)-4) with [Ir(2)(micro-Cl)(2)(cod)(2)] (cod=1,5-cyclooctadiene) afforded [Ir(Cl)(cod)[(S)-(R)-4]] (7), which reacted with AgBF(4) to form [Ir(cod)[(S)-(R)-4]]BF(4) (8). Complexes 7 and 8 reacted with iodide to yield [Ir(I)(cod)[(S)-(R)-4]] (9). When 9 was treated with one and two equivalents of HBF(4), two isomers of the cationic Ir(III) iodo hydrido complex [Ir(I)(H)(cod)[(S)-(R)-4]]BF(4) were solated (10 and 11, respectively). Complex 9 was oxidized with one equivalent of I(2) to give the iodo-bridged dinuclear species [Ir(2)I(2)(micro-I)(3)[(S)-(R)-4](2))]I (12). [Ir(2)(micro-Cl)(2)(coe)(4)] (coe=cyclooctene) reacted with (S)-(R)-4 to yield the chloro-bridged dinuclear complex [Ir(2)(micro-Cl)(2)[(S)-(R)-4](2)] (13). Complexes 7-12 were structurally characterized by single-crystal X-ray diffraction and tested as single-component catalyst precursors for enantioselective hydrogenation of MEA-imine. Complex 10 and dinuclear complex 12 gave the best catalytic results. Efforts were also directed at isolating substrate- or product-catalyst adducts: Treatment of 8 with 2,6-dimethylphenyl-1'-methyl-2'-methoxyethylimine (DMA-imine, 14, a model for 1) under H(2) allowed four isomers of [Ir(H)(2)[(S)-(R)-4](14)]BF(4) (18-21) to be isolated. These analytically pure isomers were fully characterized by 2D NMR techniques. X-ray structural analysis of an Ir(I)-imine adduct, namely, [Ir(C(2)H(4))(2)(14)]BF(4) (25), which was prepared by reacting [IrCl(C(2)H(4))(4)] with [Ag(14)(2)]BF(4) (16), confirmed the kappa(2) coordination mode of imine 14.     

Exploring stereogenic phosphorus: synthetic strategies for diphosphines containing bulky,highly symmetric substituents

Diphosphine ligands bearing highly symmetric, bulky substituents at a stereogenic P atom were prepared, exploiting established protocols, which include the use of chiral synthons such as 3,4-dimethyl-2,5-diphenyl-1,3,2-oxazaphospholidine-2-borane (3a) and phenylmethylchlorophosphine borane (10) and the enantioselective deprotonation of dimethylarylphosphine boranes. However, only (Bu(t)())(Me)PCH(2)CH(2)P(Bu(t)Me (8a) could be prepared from 3a. The diphosphines (S,S)-1,2-bis(mesitylmethylphosphino)ethane, ((S,S)-8b) and (S,S)-1,2-bis(9-anthrylmethylphosphino)ethane ((S,S)-8c), which contain 2,6-disubstituted aryl P-substituents, were prepared by Evans' sparteine-assisted enantioselective deprotonation of P(Ar)(Me)(2)(BH(3)) (Ar = mesityl or 9-anthryl), but the enantioselectivity did not exceed 37% ee. The asymmetrically substituted, methylene-bridged diphosphine (2R,4R)-(Ph)(CH(3))PCH(2)P(Mes)(CH(3)) ((2R,4R)-12) (Mes = mesityl) was prepared by the newly developed stereospecific reaction of the enantiomerically pure chlorophosphine borane PCl(Ph)(Me)(BH(3)) (10) with the racemic, monolithiated dimethylmesitylphosphine borane P(Mes)(Me)(CH(2)Li)(BH(3)). Diastereomerically pure (2R,4R)-12 was obtained with 86% ee. The rhodium(I) derivatives [Rh(COD)(P-P)]BF(4) containing the diphosphine ligands 8a, 8b, and 12, as well as the previously reported (S,S)-1,2-bis(1-naphthylphenylphosphino)ethane ((S,S)-8d), were prepared and tested in the enantioselective catalytic hydrogenation of acetamidocinnamates. The best catalytic result (98.6% ee) was obtained with [Rh(COD)(8d)](+) as catalyst and methyl Z-alpha-acetamidocinnamate as substrate. Some of the catalytic results are discussed in terms of the preferred conformations of the substituents at phosphorus, as calculated by molecular modeling.     

2-phosphanylphenolate nickel catalysts for the polymerization of ethylene

The previously unknown methallylnickel 2-diorganophosphanylphenolates (R=Ph, cHex) were synthesized and found to catalyze the polymerization of ethylene. To explore the potential for ligand-tuning, a variety of P-alkyl- and P-phenyl-2-phosphanylphenols was synthesized and allowed to react with [Ni(cod)(2)] (cod=1,5-cyclooctadiene) or with NiBr(2).DME and NaH. The complexes formed in situ with [Ni(cod)(2)] are generally active as ethylene polymerization catalysts with all the ligands tested, whereas the latter systems are inactive when 2-dialkylphosphanylphenols are applied. M(w) values, ranging from about 1000 to about 100000 g mol(-1), increase for various R(2)P groups in the order R=Ph相似文献   

A series of dinuclear homo- and heterometallic complexes with two or three bridging sulfido ligands derived from the tungsten tris(sulfido) complex [Et(4)N][(Me(2)Tp)WS(3)] (Me(2)Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate)

The generation of heterobimetallic complexes with two or three bridging sulfido ligands from mononuclear tris(sulfido) complex of tungsten [Et(4)N][(Me(2)Tp)WS(3)] (1; Me(2)Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate) and organometallic precursors is reported. Treatment of 1 with stoichiometric amounts of metal complexes such as [M(PPh(3))(4)] (M = Pt, Pd), [(PtMe(3))(4)(micro(3)-I)(4)], [M(cod)(PPh(3))(2)][PF(6)] (M = Ir, Rh; cod = 1,5-cyclooctadiene), [Rh(cod)(dppe)][PF(6)] (dppe = Ph(2)PCH(2)CH(2)PPh(2)), [CpIr(MeCN)(3)][PF(6)](2) (Cp = eta(5)-C(5)Me(5)), [CpRu(MeCN)(3)][PF(6)], and [M(CO)(3)(MeCN)(3)] (M = Mo, W) in MeCN or MeCN-THF at room temperature afforded either the doubly bridged complexes [Et(4)N][(Me(2)Tp)W(=S)(micro-S)(2)M(PPh(3))] (M = Pt (3), Pd (4)), [(Me(2)Tp)W(=S)(micro-S)(2)M(cod)] (M = Ir, Rh (7)), [(Me(2)Tp)W(=S)(micro-S)(2)Rh(dppe)], [(Me(2)Tp)W(=S)(micro-S)(2)RuCp] (10), and [Et(4)N][(Me(2)Tp)W(=S)(micro-S)(2)W(CO)(3)] (12) or the triply bridged complexes including [(Me(2)Tp)W(micro-S)(3)PtMe(3)] (5), [(Me(2)Tp)W(micro-S)(3)IrCp][PF(6)] (9), and [Et(4)N][(Me(2)Tp)W(micro-S)(3)Mo(CO)(3)] (11), depending on the nature of the incorporated metal fragment. The X-ray analyses have been undertaken to clarify the detailed structures of 3-5, 7, and 9-12.     

Coordination chemistry of phosphanyl amino acids: solid state and solution structures of neutral and cationic rhodium complexes

Copper phosphide or arsenide complexes, [Cu(EPh(2))(neo)] (E = P, As, neo = 2,9-dimethyl-1,10-phenanthroline; trivial name: neocuprine) react selectively with the N-protected brominated serine derivatives, 2-(S)-(alkoxycarbonylamino)-3-bromomethylpropionates ((ROCO)SerBr, : R = PhCH(2), : tBu, : Me) to give the corresponding phosphanylated or arsanylated amino acids, (ROCO)SerPhos (: Phos = PPh(2)) and (Z)SerArs (Ars = AsPh(2), Z = PhCH(2)OCO). The dipeptide (Z)AlaSerPhos was likewise prepared. The phosphanes , and the arsane reacted cleanly with [Rh(2)(micro-Cl)(2)(cod)(2)] to give the rhodium(I) complexes [RhCl(cod)((Z)SerPhos)] , [RhCl(cod)((Boc)SerPhos)] (Boc = tBuOCO), [RhCl(cod)((Z)AlaSerPhos)] , and [RhCl(cod)((Z)SerArs)] which were characterized by X-ray diffraction studies. A common structural feature is an intramolecular (N)H[dot dot dot]Cl(Rh)-hydrogen bridge which according to NMR investigations remains intact in solution. The abstraction of chloride from the coordination sphere of Rh(I) in or has a profound structural impact. While in and , the ligands bind in a monodentate fashion, via the phosphorus atom only, they serve as bidentate ligands via the phosphorus centre and the peptidic C=O group in [Rh(cod)(kappa(2)-(Z)SerPhos)]PF(6) and [Rh(cod)(kappa(2)-(Z)AlaSerPhos)]PF(6). This causes also the amino acid residue structures to change from alpha-helix type in and to a beta-sheet type in both. Addition of chloride to and fully re-establishes the structures of both. The complexes [RhCl(cod)((Z)SerPhos)] and [RhCl(cod)((Boc)SerPhos)] show good activities in homogeneously catalyzed hydrogenations of olefins while the dipeptide complex is less active. Phosphane addition to greatly diminishes the catalytic activity. The cationic complex [Rh(cod)(kappa(2)-(Z)AlaSerPhos)]PF(6) shows low activity which, however, is greatly increased by addition of one equivalent of phosphane.     

Heteronuclear rhodium, palladium, platinum, and gold organoimido complexes from dinuclear organoamido rhodium precursors

Treatment of the organoamido complexes [Rh(2)(mu-4-HNC(6)H(4)Me)(2)(L(2))(2)] (L(2) = 1,5-cyclooctadiene (cod), L = CO) with nBuLi gave solutions of the organoimido species [Li(2)Rh(2)(mu-4-NC(6)H(4)Me)(2)(L(2))(2)]. Further reaction of [Li(2)Rh(2)(mu-4-NC(6)H(4)Me)(2)(cod)(2)] with [Rh(2)(mu-Cl)(2)(cod)(2)] afforded the neutral tetranuclear complex [Rh(4)(mu-4-NC(6)H(4)Me)(2)(cod)(4)] (2), which rationalizes the direct syntheses of 2 from [Rh(2)(mu-Cl)(2)(cod)(2)] and Li(2)NC(6)H(4)Me. Reactions of [Li(2)Rh(2)(mu-4-NC(6)H(4)Me)(2)(CO)(4)] with chloro complexes such as [Rh(2)(mu-Cl)(2)(CO)(4)], [MCl(2)(cod)] (M = Pd, Pt), and [Ru(2)(mu-Cl)(2)Cl(2)(p-cymene)(2)] afforded the homo- and heterotrinuclear complexes PPN[Rh(3)(mu-4-NC(6)H(4)Me)(2)(CO)(6)] (5; PPN=bis(triphenylphosphine)iminium), [(CO)(4)Rh(2)(mu-4-NC(6)H(4)Me)(2)M(cod)] (M = Pd (6), Pt(7)) and [(CO)(4)Rh(2)(mu-4-NC(6)H(4)Me)(2)Ru(p-cymene)] (8), while the reaction with [AuCl(PPh(3))] gave the tetranuclear compound [(CO)(4)Rh(2)(mu--4-NC(6)H(4)Me)(2)[Au(PPh(3))](2)] (9). The structures of complexes 6, 8, and 9 were determined by X-ray diffraction studies. The anion of 5 reacts with [AuCl(PPh(3))] to give the butterfly cluster [[Rh(3)(mu-4-NC(6)H(4)Me)(2)(CO)(6)]Au(PPh(3))] (10), in which the Au atom is bonded to two rhodium atoms. Reaction of the anion of 5 with [Rh(cod)(NCMe)(2)](BF(4)) gave the tetranuclear complex [Rh(4)(mu-4-NC(6)H(4)Me)(2)(CO)(6)(cod)] (11) in which the Rh(cod) fragment is pi-bonded to one of the arene rings, while the reaction of the anion of 5 with [PdCl(2)(cod)] afforded the heterotrinuclear complex 6 through a metal exchange process.     

Ru-catalyzed highly enantioselective hydrogenation of beta-alkyl-substituted beta-(acylamino)acrylates

Highly enantioselective hydrogenation of beta-alkyl-substituted (E)-beta-(acylamino)-acrylates catalyzed by Ru((R)-Xyl-P-Phos)(C(6)H(6))Cl(2) complex (cat. 1c) was achieved in up to 99.7% ee. Moderate to good enantioselectivities in the hydrogenation of corresponding (Z)-isomers in the presence of [Rh((R)-Xyl-P-Phos)(COD)]BF(4) (cat. 2c) were also obtained. The results demonstrated that the electronic and steric properties of the dipyridylphosphine ligands as well as the different transition metal ions have significant influences on the catalytic properties in the hydrogenation of beta-(acylamino)acrylates.     

Charging and deforming the pybox ligand: enantiomerically pure double helices and their interconversion

Reaction of pyrrole-2,5-biscarbonitrile (1) with an excess of (S)- or (R)-valinol in boiling chlorobenzene selectively yielded the two enantiomeric bis(oxazolinyl)pyrroles (S,S)-bis[2-(4,4'-diisopropyl-4,5-dihydrooxazolyl)]pyrrole ("S,S-iproxpH", 2 a) and (R,R)-bis[2-(4,4'-diisopropyl-4,5-dihydrooxazolyl)]pyrrole ("R,R-iproxpH", 2 b), respectively. Lithiation of 2 a and 2 b at -78 degrees C and reaction with an equimolar amount of [PdCl(2)(cod)] (cod=1,5-cyclooctadiene) gave the helical dinuclear palladium complexes (M)-[PdCl(S,S-iproxp)](2) (3 a) and (P)-[PdCl(S,S-iproxp)](2) (3 b) as well as (P)-[PdCl(R,R-iproxp)](2) (4 a) and (M)-[PdCl(R,R-iproxp)](2) (4 b). Reaction of a 1:1 mixture of lithiated 2 a and 2 b with an equimolar amount of [PdCl(2)(cod)] gave a mixture of the homochiral complexes 3 a,b and 4 a,b along with the racemic mixture of the heterochiral complex [Pd(2)Cl(2)(S,S-iproxp)(R,R-iproxp)] (5). The double helical structure as well as the absolute configuration of these neutral dinuclear palladium complexes was confirmed by X-ray diffraction studies of all five complexes. One of the oxazolyl units and the anionic pyrrolide occupy two coordination sites in an approximately square-planar ligand arrangement at the Pd centers whereas the second oxazolyl ring is twisted out of this plane and binds to the second metal center. The heterochiral complex 5 does not possess any element of molecular symmetry. The P-helical complexes 3 b and 4 a display a positive CD at 310 nm and a weaker negative CD at 350 nm, while the compounds possessing M-helicity have the corresponding mirror image CD spectra. Complexes 3 a and 4 a have an additional weak long wavelength CD feature between 380 and 420 nm which is absent in the spectra of 3 b and 4 b. Upon heating a solution of 3 b, interconversion to the diastereomer of opposite helicity 3 a sets in, for which a first-order rate law with respect to the concentration of the complex was established; activation parameters: DeltaH( not equal )=68 kJ mol(-1), DeltaS( not equal )=-99 J mol(-1) K(-1). A cross-over experiment monitored by (1)H NMR spectroscopy also gave the racemate of the mixed-ligand complex 5: (P)-[Pd(2)Cl(2)(S,S-iproxp)(R,R-iproxp)] and (M)-[Pd(2)Cl(2)(S,S-iproxp)(R,R-iproxp)] indicating an intermolecular exchange involving mononuclear [PdCl(iproxp)] complex fragments.     

Chiral phosphane alkenes (PALs): simple synthesis, applications in catalysis, and functional hemilability

A simple synthesis of a chiral phosphane alkene (PAL) involves: 1) palladium-catalyzed Suzuki coupling of 10-bromo-5H-dibenzo[a,d]cyclohepten-5-ol (1) with phenylboronic acid to give quantitatively 10-phenyl-5H-dibenzo[a,d]cyclohepten-5-ol (2); 2) reaction of 2 with Ph(2)PCl under acidic conditions to give a racemic mixture of the phosphane oxide (10-phenyl-5H-dibenzo[a,d]cyclohepten-5-yl)diphenylphosphane oxide ((Ph)troppo(Ph), 3), which is separated into enantiomers by using high-pressure liquid chromatography (HPLC) on a chiral column; 3) reduction with trichlorosilane to give the enantiomerically pure phosphanes (R)- and (S)-(10-phenyl-5H-dibenzo[a,d]cyclohepten-5-yl)diphenylphosphane ((Ph)tropp(Ph), 4). This highly rigid, concave-shaped ligand serves as a bidentate ligand in Rh(I) and Ir(I) complexes. Catalysts prepared from [Rh(2)(mu(2)-Cl)(2)(C(2)H(4))(4)] and (S)-4 have allowed the efficient enantioselective 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyls (Hayashi-Miyaura reaction) (5-0.1 mol % catalyst, up to 95% ee). The iridium complex (S,S)-[Ir((Ph)tropp(Ph))(2)]OTf ((S,S)-6; OTf=SO(3)CF(3)) has been used as a catalyst in the hydrogenation of various nonfunctionalized and functionalized olefins (turnover frequencies (TOFs) of up to 4000 h(-1)) and moderate enantiomeric excesses have been achieved (up to 67% ee). [Ir((Ph)tropp(Ph))(2)]OTf reversibly takes up three equivalents of H(2). The highly reactive octahedral [Ir(H)(2)(OTf)(CH(2)Cl(2))(H(2)-(Ph)tropp(Ph))(2)] could be isolated and contains two hydrogenated monodentate H(2)-(Ph)tropp(Ph) phosphanes, one CH(2)Cl(2) molecule, one triflate anion, and two hydrides. Based on this structure and extensive NMR spectroscopic studies, a mechanism for the hydrogenation reactions is proposed.     

Dinuclear rhodium and iridium complexes with mixed amido/methoxo and amido/hydroxo bridges

The reactions of [[M(mu-OMe)(cod)](2)] (M = Rh, Ir; cod = 1,5- cyclooctadiene) with p-tolylamine, alpha-naphthylamine, and p-nitroaniline gave complexes with mixed-bridging ligands, [[M(cod)](2)(mu-NHAr)(mu-OMe)]. Similarly, the related complexes [[Rh(cod)](2)(mu-NHAr)(mu-OH)] were prepared from the reactions of [[Rh(mu-OH)(cod)](2)] with p-tolylamine, alpha-naphthylamine, and p-nitroaniline. The reactions of [[Rh(mu-OR)(cod)](2)] (R = H, Me) with o-nitroaniline gave the mononuclear complex [Rh(o-NO(2)C(6)H(4)NH)(cod)]. The syntheses of the amido complexes involve a proton exchange reaction from the amines to the methoxo or hydroxo ligands and the coordination of the amide ligand. These reactions were found to be reversible for the dinuclear complexes. The structure of [[Rh(cod)](2)(mu-NH[p-NO(2)C(6)H(4)])(mu-OMe)] shows two edge-shared square-planar rhodium centers folded at the edge with an anti configuration of the bridging ligands. The complex [[Rh(cod)](2)(mu-NH[alpha-naphthyl])(mu-OH)] cocrystallizes with [[Rh(mu-OH)(cod)](2)] and THF, forming a supramolecular aggregate supported by five hydrogen bridges in the solid state. In the mononuclear [Rh(o-NO(2)C(6)H(4)NH)(cod)] complex the o-nitroamido ligand chelates the rhodium center through the amido nitrogen and an oxygen of the nitro group.