Carbene- and carbyne-like behavior of the Mo-P multiple bond in a dimolybdenum complex inducing trigonal-pyramidal coordination of a phosphinidene ligand

The phosphinidene complex [Mo2Cp(micro-kappa1:kappa1,eta5-PC5H4)(CO)2(eta6-R*H)] (2; Cp = eta5-C5H5; R* = 2,4,6-C6H2tBu3) has substantially different Mo-P bonds and displays a high reactivity located at the short Mo-P bond. Sideways cycloaddition or addition processes are observed toward RCCR, HCl, and [Fe2(CO)9], to give respectively metallacyclobutene and arylphosphide-bridged and heterometallic phosphinidene-bridged derivatives, a behavior reminiscent of the nucleophilic mononuclear phosphinidene complexes (carbene-like behavior), which is in good agreement with the ground-state electronic structure of 2 derived from density functional theory calculations. However, the reaction of 2 with [Co2(CO)8] implies the addition of two cobalt fragments to its short Mo-P bond and thus reveals a carbyne-like behavior of compound 2. In most of the new products, the P atom displays an unprecedented trigonal-pyramidal-like environment, instead of the expected tetrahedral distribution of bonds.     

Copper(I) chloride initiated decomposition of 7-phosphanorbornadiene. Evidence for a solvent-assisted catalytic mechanism

Density functional theory is used to explore the mechanism of the copper(I)-chloride-catalyzed decomposition of W(CO)(5)-complexed 7-phosphanorbornadiene and the subsequent olefin trapping of the terminal phosphinidene complex. CuCl lowers the activation barrier by interacting directly with the breaking P-C bond. Contrary to the prevailing notion that a free terminal phosphinidene complex (W(CO)(5)=PR) is generated in the CuCl-catalyzed cheletropic elimination of the 7-phosphanorbornadiene-W(CO)(5) complex, the present mechanism suggests that CuCl is attached to the terminal phosphinidene. Furthermore, a "chloride shuttle" takes place where the chloride first migrates to the phosphorus center and then is returned back to the copper center by the incoming olefin in an S(N)2 reaction step. When the substituent on phosphorus is a phenyl group (R = Ph), the uncatalyzed reaction has an activation barrier of 17.9 kcal/mol, which is reduced by 10.9 kcal/mol on including the CuCl catalyst. The CuCl-catalyzed decomposition of 7-phosphanorbornadiene followed by olefin trapping of the terminal phosphinidene complex has a close parallel with the Cu(I)-catalyzed cyclopropanation reaction of diazoalkane. In both catalyzed reactions, copper(I) is coordinated to the phosphinidene/carbene as a Lewis acid, while a Lewis base is displaced from the phosphorus/carbon center as the olefin is added.     

Monomeric phosphido and phosphinidene complexes of nickel

An unusual family of three-coordinate, d(8) and d(9) nickel phosphido and phosphinidene complexes containing the chelating 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand and a terminal PR(2)(-) or PR(2-) ligand have been prepared. The complexes (dtbpe)Ni[P(t-Bu)(2)] (2), [(dtbpe)Ni[=P(t-Bu)(2)](+)][PF(6)(-)] (3), [(dtbpe)Ni[=P(H)(dmp)](+)][PF(6)(-)] (5), and (dtbpe)Ni[=P(dmp)] (6) have been structurally characterized by single-crystal X-ray diffraction methods. The three-coordinate d(8) complexes exhibit Ni-P bond lengths and ligand geometries that indicate they participate in symmetry-allowed ligand-to-metal pi bonding involving phosphorus p-electrons and a metal-orbital of pi symmetry that lies in the Ni coordination plane. Compound 6 is a rare example of a late-transition-metal terminal phosphinidene complex.     

Metal-template-directed synthesis of diphosphorus compounds through intramolecular phosphinidene additions

Heating the nonchelating cis-bis-7-phosphanorbornadiene-[Mo(CO)4] complex (13) results in the thermal decomposition of one of the 7-phosphanorbornadiene groups. The phosphinidene thus generated adds intramolecularly to a C=C bond of the other ligand to give the novel diphosphorus complex 14. This reaction constitutes a metal-template-directed synthesis. Likewise, the intramolecular phosphinidene addition to the C=C bond of a Mo-phospholene ligand affords the diphos complex 18. Its crystal structure exhibits an extremely small P-Mo-P bite-angle for a five-membered chelate ring. The similar intramolecular 1,2-addition to a C=C bond of a phosphole ligand gives a highly strained, unstable intermediate product. Scission of its P-Mo bond generates a free coordination site, which is then occupied by either CO or a phosphole to yield complexes 22 and 23, respectively. The analogous intermolecular addition of [PhPW(CO)5] to a [phosphole-W(CO)5] complex gives the di-[W(CO)5] complexed adduct 28. The directing effect of the metal on the intra- and intermolecular additions is discussed.     

Neutral and zwitterionic low-coordinate titanium complexes bearing the terminal phosphinidene functionality. Structural, spectroscopic, theoretical, and catalytic studies addressing the Ti-P multiple bond

Alpha-hydrogen abstraction and alpha-hydrogen migration reactions yield novel titanium(IV) complexes bearing terminal phosphinidene ligands. Via an alpha-H migration reaction, the phosphinidene ((tBu)nacnac)Ti=P[Trip](CH(2)(tBu) ((tBu)nacnac(-) = [Ar]NC((t)Bu)CHC((t)Bu)N[Ar], Ar = 2,6-(CHMe2)(2C6H3, Trip = 2,4,6-(i)Pr3C6H2) was prepared by the addition of the primary phosphide LiPH[Trip] to the nucleophilic alkylidene triflato complex ((tBu)nacnac)Ti=CH(t)Bu(OTf), while alpha-H abstraction was promoted by the addition of LiPH[Trip] to the dimethyl triflato precursor ((tBu)nacnac)Ti(CH)(2)(OTf) to afford ((tBu)nacnac)Ti=P[Trip](CH3). Treatment of ((tBu)nacnac)Ti=P[Trip](CH3) with B(C6F5)(3) induces methide abstraction concurrent with formation of the first titanium(IV) phosphinidene zwitterion complex ((tBu)nacnac)Ti=P[Trip]{CH3B(C6F5)(3)}. Complex ((tBu)nacnac)Ti=P[Trip]{CH3B(C6F5)(3)} [2 + 2] cycloadds readily PhCCPh to afford the phosphametallacyclobutene [((tBu)nacnac)Ti(P[Trip]PhCCPh)][CH3B(C6F5)(3)]. These titanium(IV) phosphinidene complexes possess the shortest Ti=P bonds reported, have linear phosphinidene groups, and reveal significantly upfielded solution 31P NMR spectroscopic resonances for the phosphinidene phosphorus. Solid state 31P NMR spectroscopic data also corroborate with all three complexes possessing considerably shielded chemical shifts for the linear and terminal phosphinidene functionality. In addition, high-level DFT studies on the phosphinidenes suggest the terminal phosphinidene linkage to be stabilized via a pseudo Ti[triple bond]P bond. Linearity about the Ti-P-C(ipso) linkage is highly dependent on the sterically encumbering substituents protecting the phosphinidene. Complex ((tBu)nacnac)Ti=P[Trip]{CH3B(C6F5))(3)} can catalyze the hydrophosphination of PhCCPh with H(2)PPh to produce the secondary vinylphosphine HP[Ph]PhC=CHPh. In addition, we demonstrate that this zwitterion is a powerful phospha-Staudinger reagent and can therefore act as a carboamination precatalyst of diphenylacetylene with aldimines.     

Modeling the syn disposition of nitrogen donors at the active sites of carboxylate-bridged diiron enzymes. Enforcing dinuclearity and kinetic stability with a 1,2-diethynylbenzene-based ligand

The syn coordination of histidine residues at the active sites of several carboxylate-rich non-heme diiron enzymes has been difficult to reproduce with small molecule model compounds. In this study, ligands derived from 1,8-naphthyridine, phthalazine, and 1,2-diethynylbenzene were employed to mimic this geometric feature. The preassembled diiron(II) complex [Fe(2)(micro-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(THF)(2)] (1), where Ar(Tol)CO(2)(-) is the sterically hindered carboxylate 2,6-di(p-tolyl)benzoate, served as a convenient starting material for the preparation of iron(II) complexes, all of which were crystallographically characterized. Use of the ligand 2,7-dimethyl-1,8-naphthyridine (Me(2)-napy) afforded the mononuclear complex [Fe(O(2)CAr(Tol))(2)(Me(2)-napy)] (2), whereas dinuclear [Fe(2)(micro-DMP)(micro-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(THF)] (3) resulted when 1,4-dimethylphthalazine (DMP) was employed. The dinuclear core of compound 3 is kinetically labile, as evidenced by the formation of [Fe(O(2)CAr(Tol))(2)(vpy)(2)] (4) upon addition of 2-vinylpyridine (vpy). The diiron analogue of 4, [Fe(2)(micro-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(vpy)(2)] (5), was prepared directly from 1. When the sterically more demanding ligand 2,6-di(4-tert-butylphenyl)benzoate (Ar(4-tBuPh)CO(2)(-)) was used, mononuclear [Fe(O(2)CAr(4)(-)(tBuPh))(2)(THF)(2)] (6) and [Fe(O(2)CAr(4)(-)(tBuPh))(2)(DMP)(2)] (7) formed. The difficulty in stabilizing a dinuclear core with these simple (N)(2)-donor ligands was circumvented by preparing a family of 1,2-diethynylbenzene-based ligands, from which were readily assembled the complexes [Fe(2)(Et(2)BCQEB(Et))(micro-O(2)CAr(Tol))(3)](OTf) (15) and [Cu(2)(Et(2)BCQEB(Et))(micro-I)(2)] (16), where Et(2)BCQEB(Et) is 1,2-bis(3-ethynyl-8-carboxylatequinoline)benzene ethyl ester. The Et(2)BCQEB(Et) framework provides both structural flexibility and the desired syn nitrogen donor geometry, thus serving as a good first-generation ligand in this class.     

The insertion of terminal phosphinidene complexes into the bh bond of amine and phosphine boranes

Push-pull complexation: Transient terminal phosphinidene complexes [RP?W(CO)(5) ] insert at 110?°C into the B?H bonds of L?BH(3) (L = Et(3) N, Ph(3) P; see scheme). The reaction is probably driven by an interaction between the nucleophilic boron and the electrophilic phosphorus.     

Strained, stable 2-aza-1-phosphabicyclo[n.1.0]alkane and -alkene Fe(CO)4 complexes with dynamic phosphinidene behavior

The synthesis of highly strained bicyclic phosphirane and phosphirene iron-tetracarbonyl complexes, that is, complexes with 2-aza-1-phosphabicyclo[n.1.0]alkanes and -alkenes (n = 3-5), is explored by using intramolecular cycloaddition of an in situ generated electrophilic phosphinidene complex, [R(iPr)NP=Fe(CO)(4)], to its C=C- and C[triple chemical bond]C-containing R substituent. Saturated bicyclic complexes 7 a-c with n = 4-2 are remarkably stable, as illustrated by the X-ray crystal structure for 7 b (n=3), yet all readily undergo retroaddition to react with phenylacetylene. Shuttling of the phosphinidene iron complex between two equivalent C=C groups is demonstrated for a 1-butene-substituted 2-aza-1-phosphabicyclo[3.1.0]hexane by selective (1)H NMR magnetization transfer from the phosphirane protons to the olefinic protons. Even the more strained unsaturated bicycles 17 a,b (n = 4,3) are surprisingly stable as illustrated by the X-ray crystal structure for 17 a (n = 4), but the smaller phosphabicyclo[3.1.0]hex-5-ene (17 c, n = 2) dimerizes to tricyclic 19 with a unique ten-membered heterocyclic ring; an X-ray crystal structure is reported. Like their saturated analogues also the bicyclic phosphirenes readily undergo retroaddition as shown by the reaction of their phosphinidene iron moiety with phenylacetylene.     

Examination of the silver colloid binding behavior of disulfide-tethered bipyridine ligands and their fac-tricarbonylrheniumI complexes

The syntheses of 2,2'-bipyridin-5-ylmethyl-5-(1,2-dithiolan-3-yl)pentanoate (L1) and N-(2,2'-bipyridin-5-ylmethyl)-5-(1,2-dithiolan-3-yl)pentanamide (L2) and their neutral fac carbonylrhenium(I) complexes [Re(L1)(CO)(3)Br] and [Re(L2)(CO)(3)Br] are reported. The electronic absorption and emission spectra of the complexes are similar to the spectrum of the reference compound [Re(bipy)(CO)(3)Br] and correlate well with the density functional theory calculations undertaken. The surface-enhanced Raman spectroscopy (SERS) spectra (excited at both 532 and 785 nm) of the ligands and complexes were examined and compared to the spectrum of ethyl 5-(1,2-dithiolan-3-yl)pentanoate (L3), revealing that there is very little contribution to the spectra of these species from the dithiolated alkyl chains. The spectra are dominated by the characteristic peaks of a metalated 2,2'-bipyridyl group, arising from the silver colloid/ion complexation, and the rhenium center. The rhenium complexes show weak SERS bands related to the CO stretches and a broad band at 510 cm(-1) assigned to Re-CO stretching. Concentration-dependent studies, measured by the relative intensity of several assigned peaks, indicate that, as the surface coverage increases, the bipyridine moiety lifts off the surface. In the case of L1 and L2, this gives rise to complexes with silver at low concentration, enhancing the signals observed, while for the tricarbonylbromorhenium complexes of these ligands, the presence of the disulfide tether allows an enhancement in the limits of detection of these surface-borne species of 20 times in the case of [ReL2(CO)(3)Br] over [Re(bipy)(CO)(3)Br].     

Synthesis and decarbonylation reactions of the triiron phosphinidene complex [Fe3Cp3(μ-H)(μ3-PPh)(CO)4]: easy cleavage and formation of P-H and Fe-Fe bonds

The binuclear phosphine complex [Fe(2)Cp(2)(μ-CO)(2)(CO)(PH(2)Ph)] (Cp = η(5)-C(5)H(5)) reacted with the acetonitrile adduct [Fe(2)Cp(2)(μ-CO)(2)(CO)(NCMe)] in dichloromethane at 293 K to give the trinuclear hydride-phosphinidene derivative [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(CO)(4)] as a mixture of cis,anti and trans isomers (Fe-Fe = 2.7217(6) ? for the cis,anti isomer). In contrast, photochemical treatment of the phosphine complex with [Fe(2)Cp(2)(CO)(4)] gave the phosphide-bridged complex trans-[Fe(3)Cp(3)(μ-PHPh)(μ-CO)(2)(CO)(3)] as the major product, along with small amounts of the binuclear hydride-phosphide complexes [Fe(2)Cp(2)(μ-H)(μ-PHPh)(CO)(2)] (cis and trans isomers), which are more selectively prepared from [Fe(2)Cp(2)(CO)(4)] and PH(2)Ph at 388 K. The photochemical decarbonylation of either of the mentioned triiron compounds led reversibly to three different products depending on the reaction conditions: (a) the 48-electron phosphinidene cluster [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(μ-CO)(2)] (Fe-Fe = 2.592(2)-2.718(2) ?); (b) the 50-electron complex [Fe(3)Cp(3)(μ-H)(μ(3)-PPh)(μ-CO)(CO)(2)], also having carbonyl- and hydride-bridged metal-metal bonds (Fe-Fe = 2.6177(3) and 2.7611(4) ?, respectively); and (c) the 48-electron phosphide cluster [Fe(3)Cp(3)(μ-PHPh)(μ(3)-CO)(μ-CO)(2)], an isomer of the latter phosphinidene complex now having three intermetallic bonds (Fe-Fe = 2.5332(8)-2.6158(8) ?).     

Electrophilic Terminal‐Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

Electrophilic and nucleophilic terminal‐phosphinidene complexes are compared in terms of electronic structures and reactivities. Various precursors of the unstable electrophilic species [R−P−M] (M=Cr, Mo, W(CO)₅ and Fe(CO)₄) are discussed. The addition reactions of the electrophilic phosphinidene complexes with Lewis bases, insertion reactions into O−H, N−H, and activated C−H bonds, and cycloaddition reactions with double and triple bonds are described, as well as some rearrangements and autocondensations. Various applications to the synthesis of new organophosphorus molecules are discussed and techniques available for demetallation are given.     

Mixed nitrosyl/phosphinidene and nitrene/phosphinidene clusters of ruthenium

Reaction of the aminophosphinidene complex [Ru5(CO)15(mu 4-PNPri2)] 1 with [PPN][NO2] (PPN = Ph3P=N=PPh3) led to the mixed nitrosyl/phosphinidene cluster complex [PPN][Ru5(CO)13(mu-NO)(mu 4-PNPri2)] 2 which is transformed into the novel nitrene/phosphinidene cluster [Ru5(CO)10(mu-CO)2(mu 3-CO)(mu 4-NH)(mu 3-PNPri2)] 3 via treatment with triflic acid.     

Reaction of a terminal phosphinidene complex with azulenes: eta1-complexes, C--H bond insertions, and 1,4-adducts

Reaction of an in situ generated phosphinidene complex [PhPW(CO)(5)] with the aromatic azulene and guaiazulene leads to unexpected 1,4-adducts of the seven-membered ring and to C--H bond insertion of the five-membered ring. A DFT analysis suggests that the reaction is initiated by formation of a eta(1)-complex between the phosphinidene and the five-membered ring of the aromatic substrate. Four conformations of this complex were identified. Two convert without barrier to the slightly more stable syn- and anti-1,2-adducts. These undergo pericyclic 1,7-sigmatropic rearrangements with remarkably low barriers to give 1,4-adducts, with an inverted configuration at the phosphorus center. An X-ray crystal structure is presented for one of the 1,4-adducts of guaiazulene. The other two eta(1)-complexes insert with modest barriers into a C--H bond of the five-membered ring.     

Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.     

Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn3(CO)6(mu-eta2-SCH2CH2CH2S)3

Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.     

Activation of H-H and H-O bonds at phosphorus with diiron complexes bearing pyramidal phosphinidene ligands

The complex [Fe(2)Cp(2)(μ-PMes*)(μ-CO)(CO)(2)] (Mes* = 2,4,6-C(6)H(2)(t)Bu(3)), which in the solid state displays a pyramidal phosphinidene bridge, reacted at room temperature with H(2) (ca. 4 atm) to give the known phosphine complex [Fe(2)Cp(2)(μ-CO)(2)(CO)(PH(2)Mes*)] as the major product, along with small amounts of other byproducts arising from the thermal degradation of the starting material, such as the phosphindole complex [Fe(2)Cp(2)(μ-CO)(2)(CO){PH(CH(2)CMe(2))C(6)H(2)(t)Bu(2)}], the dimer [Fe(2)Cp(2)(CO)(4)], and free phosphine PH(2)Mes*. During the course of the reaction, trace amounts of the mononuclear phosphide complex [FeCp(CO)(2)(PHMes*)] were also detected, a compound later found to be the major product in the carbonylation of the parent phosphinidene complex, with this reaction also yielding the dimer [Fe(2)Cp(2)(CO)(4)] and the known diphosphene Mes*P═PMes*. The outcome of the carbonylation reactions of the title complex could be rationalized by assuming the formation of an unstable tetracarbonyl intermediate [Fe(2)Cp(2)(μ-PMes*)(CO)(4)] (undetected) that would undergo a fast homolytic cleavage of a Fe-P bond, this being followed by subsequent evolution of the radical species so generated through either dimerization or reaction with trace amounts of water present in the reaction media. A more rational synthetic procedure for the phosphide complex was accomplished through deprotonation of the phosphine compound [FeCp(CO)(2)(PH(2)Mes*)](BF(4)) with Na(OH), the latter in turn being prepared via oxidation of [Fe(2)Cp(2)(CO)(4)] with [FeCp(2)](BF(4)) in the presence of PH(2)Mes*. To account for the hydrogenation of the parent phosphinidene complex it was assumed that, in solution, small amounts of an isomer displaying a terminal phosphinidene ligand would coexist with the more stable bridged form, a proposal supported by density functional theory (DFT) calculations of both isomers, with the latter also revealing that the frontier orbitals of the terminal isomer (only 5.7 kJ mol(-1) above of the bridged isomer, in toluene solution) have the right shapes to interact with the H(2) molecule. In contrast to the above behavior, the cyclohexylphosphinidene complex [Fe(2)Cp(2)(μ-PCy)(μ-CO)(CO)(2)] failed to react with H(2) under conditions comparable to those of its PMes* analogue. Instead, it slowly reacted with HOR (R = H, Et) to give the corresponding phosphinous acid (or ethyl phosphinite) complexes [Fe(2)Cp(2)(μ-CO)(2)(CO){PH(OR)Mes*}], a behavior not observed for the PMes* complex. The presence of BEt(3) increased significantly the rate of the above reaction, thus pointing to a pathway initiated with deprotonation of an O-H bond of the reagent by the basic P center of the phosphinidene complex, this being followed by the nucleophilic attack of the OR(-) anion at the P site of the transient cationic phosphide thus formed. The solid-state structure of the cis isomer of the ethanol derivative was determined through a single crystal X-ray diffraction study (Fe-Fe = 2.5112(8) ?, Fe-P = 2.149(1) ?).     

Selective diphosphine ligand chelation and pi bond coordination in CoRu(CO)7(mu-PPh2): kinetics and X-ray structure of CoRu(CO)4(mu-bma)(mu-PPh2)

Thermolysis of CoRu(CO)7(mu-PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(mu-P-P)(mu-PPh2) [where P-P = bma (3a), bpcd (3b)] along with trace amounts of the known complex CoRu(CO)6(PPh3)(mu-PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(mu-P-P)(mu-PPh2) [where P-P = bma (2a), bpcd (2b)] have been prepared by separate routes (mild thermolysis and Me3NO activation) and studied for their conversion to CoRu(CO)4(mu-P-P)(mu-PPh2). The penta- and tetracarbonyl complexes have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2a-->3a and of 2b-->3b were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters (2a-->3a, delta H++ = 29.2 +/- 1.4 kcal mol-1 and delta S++ = 8.2 +/- 3.8 eu; 2b-->3b, delta H++ = 27.7 +/- 0.6 kcal mol-1 and delta S++ = 1.4 +/- 1.6 eu), a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(mu-bma)(mu-PPh2) (3a), as determined by X-ray crystallography, reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride pi bond is coordinated to the cobalt atom.     

Mechanistic investigation of CO2 hydrogenation by Ru(II) and Ir(III) aqua complexes under acidic conditions: two catalytic systems differing in the nature of the rate determining step

Ruthenium aqua complexes [(eta(6)-C(6)Me(6))Ru(II)(L)(OH(2))](2+) {L = bpy (1) and 4,4'-OMe-bpy (2), bpy = 2,2'-bipyridine, 4,4'-OMe-bpy = 4,4'-dimethoxy-2,2'-bipyridine} and iridium aqua complexes [Cp*Ir(III)(L)(OH(2))](2+) {Cp* = eta(5)-C(5)Me(5), L = bpy (5) and 4,4'-OMe-bpy (6)} act as catalysts for hydrogenation of CO(2) into HCOOH at pH 3.0 in H(2)O. The active hydride catalysts cannot be observed in the hydrogenation of CO(2) with the ruthenium complexes, whereas the active hydride catalysts, [Cp*Ir(III)(L)(H)](+) {L = bpy (7) and 4,4'-OMe-bpy (8)}, have successfully been isolated after the hydrogenation of CO(2) with the iridium complexes. The key to the success of the isolation of the active hydride catalysts is the change in the rate-determining step in the catalytic hydrogenation of CO(2) from the formation of the active hydride catalysts, [(eta(6)-C(6)Me(6))Ru(II)(L)(H)](+), to the reactions of [Cp*Ir(III)(L)(H)](+) with CO(2), as indicated by the kinetic studies.