Synthesis, structure, and reactivity of mononuclear RE(I) oximato complexes

Complexes [Re(ONCMe2)(CO)3(bipy)] (1) and [Re(ONCMe2)(CO)3(phen)] (2), synthesized by reaction of the respective triflato precursors [Re(OTf)(CO)3(N-N)] (N-N = bipy, phen) with KONCMe2, feature O-bonded monodentate oximato ligands. Compound [Re(CO)3(phen)(HONCMe2)]BAr'4 (3), with a monodentate N-bonded oxime ligand, was prepared by reaction of [Re(OTf)(CO)3(phen)], HONCMe2, and NaBAr'4. Deprotonation of 3 afforded 2. The oximato complexes reacted with p-tolylisocyanate, p-tolylisothiocyanate, maleic anhydride, and tetracyanoethylene, affording the products of the insertion of the electrophile into the Re-O bond, compounds 4-7. One representative of each type of compound was fully characterized, including single-crystal X-ray diffraction. The reactions of 1 and 2 with dimethylacetylenedicarboxylate were found to involve first an insertion as the ones mentioned above but followed by incorporation of water, loss of acetone, and formation of the charge-separated neutral amido complexes 9 and 10. The structure of 9 and 10 was determined by X-ray diffraction, and key features of their electronic distribution were studied using a topological analysis of the electron density as obtained from the Fourier map.     

Low-temperature N-O bond cleavage of nitrogen monoxide in heterometallic carbonyl complexes. An experimental and theoretical study

The reaction of Na[RuCp(CO) 2] with [MnCp'(CO) 2(NO)]BF 4 gives the corresponding heterometallic derivative [MnRuCpCp'(mu-CO) 2(CO)(NO)] (Cp = eta (5)-C 5H 5; Cp' = eta (5)-C 5H 4Me). In contrast, the group 6 metal carbonyl anions [MCp(CO) 2L] (-) (M = Mo, W; L = CO, P(OMe) 3, PPh 3) react with the Mn and Re complexes [M'Cp'(CO) 2(NO)]BF 4 to give the heterometallic derivatives [MM'CpCp'(mu-N)(CO) 3L] having a nitride ligand linearly bridging the metal centers (W-N = 1.81(3) A, N-Re = 1.97(3) A, W-N-Re = 179(1) (o), in [WReCpCp'(mu-N)(CO) 3{P(OMe) 3}]). Density-functional theory calculations on the reactions of [WCp(CO) 3] (-) and [RuCp(CO) 2] (-) with [MnCp(CO) 2(NO)] (+) revealed a comparable qualitative behavior. Thus, two similar and thermodynamically allowed reaction pathways were found in each case, one implying the displacement of CO from the cation and formation of a metal-metal bond, the other implying the cleavage of the N-O bond of the nitrosyl ligand and release of a carbonyl from the anion as CO 2. The second pathway is more exoergonic and is initiated through an orbitally controlled attack of the anion on the N atom of the NO ligand in the cation. In contrast, the first pathway is initiated through a charge-controlled attack of the anion to the C atom of a CO ligand in the cation. The CO 2-elimination pathway requires at the intermediate stages a close approach of the NO and CO ligands, which is more difficult for the Ru compound because of its lower coordination number (compared to W). This effect, when combined with a stronger stabilization of the initial intermediate in the Ru reaction, makes the CO 2-elimination pathway slower in that case.     

Syntheses and chemistry of hypervalent cyclo-R4Sb4, cyclo-(RSbE)n[R = 2-(Me2NCH2)C6H4, E = O, S] and precursors

The cyclostibane R(4)Sb(4)(1)(R = 2-(Me(2)NCH(2))C(6)H(4)) was synthesized by reduction of RSbCl(2) with Mg in THF or with Na in liquid NH(3). The reaction of 1 with [W(CO)(5)(THF)] gives the stibinidene complex RSb[W(CO)(5)](2)(2). RSbCl(2) and (RSbCl)(2)E [E = O (6), E = S (8)] react with KOH or Na(2)S in toluene/water to give the heterocycles (RSbE)(n)[E = O, n= 3 (3); E = S, n= 2 (4)]. The chalcogeno-bridged compounds of the type (RSbCl)(2)E [E = O (6), E = S (8)] were synthesized by reaction of RSbCl(2) with KOH or Na(2)S in toluene/water, but also by reaction of RSbCl(2) with the heterocycles (RSbE)(n). The compounds (RSbI)(2)O (7) and (RSbBr)(2)S (9) were prepared via halogen-exchange reactions between (RSbCl)(2)E and NaI (E = O) or KBr (E = S) or by reactions between RSbI(2) and KOH or RSbBr(2) and Na(2)S. The reaction of cyclo-(RSbS)(2) with W(CO)(5)(THF) in THF results in trapping of the cis isomer in cyclo-(RSbS)(2)[W(CO)(5)](5). The solution behaviour of the compounds was investigated by (1)H and (13)C NMR spectroscopy. The molecular structures of compounds 1-7 and 9 were determined by single-crystal X-ray diffraction.     

Bis(1 degree-amino)cyclodistib(III)azanes: the first structural characterization of cis and trans isomers of a single cyclodipnict(III)azane

The dichlorocyclodistib(III)azane [ClSb(mu-NtBu)]2 (1) has been shown to exist as the cis isomer in the solid state. A series of bis(1 degree-amino)cyclodistib(III)azanes [R'NHSb(mu-NtBu)]2 (2, R' = tBu; 3, R' = Dipp; 4, R' = Dmp) has been prepared by the reaction of 1 with 2 equiv. of LiNHR'. On the basis of NMR solution spectra, all three derivatives are formed as a mixture of cis and trans isomers. In the case of 3, the structures of both the cis and trans isomers have been determined by X-ray crystallography; cis-3 adopts an endo, endo arrangement for the amido protons of the DippNH groups. Isomerization of trans-3 into cis-3 occurs slowly in solution. Deprotonation of 2 with 2 equiv. of nBuNa or trans-3 with nBuLi produces [Na2Sb2(mu-NtBu)4] (5) and [Li2Sb2(mu-NtBu)2(mu-NDipp)2] (6), whose solvated cubane structures were established by X-ray crystallography. In contrast, the reaction of cis-3 with 2 equiv. of nBuLi produces the tricyclic compound [Li2Sb(mu-NtBu)2(mu-NDipp)(mu-NHDipp)] (7).     

Mixed-metal cluster chemistry. 28. Core enlargement of tungsten-iridium clusters with alkynyl, ethyndiyl, and butadiyndiyl reagents

Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.     

Clusters as Ligands. 4. Synthesis, Structure, and Characterization of the Tungsten(II)-Tungsten(III) Cluster Carboxylate {[Na][W(2){OOCCCo(3)(CO)(9)}(2)(OOCCF(3))(4)(THF)(2)]}(2)

The reaction of W(2)(OOCCF(3))(4) with (CO)(9)Co(3)CCOOH and Na[OOCCF(3)] in a nonpolar solvent mixture leads to the formation of the cluster of clusters {[Na][W(2){OOCCCo(3)(CO)(9)}(2)(OOCCF(3))(4)(THF)(2)]}(2), 1, in 40% yield. The structure of 1.3C(6)H(5)CH(3) in the solid state corresponds to a dimer of W(2) dinuclear complexes (monoclinic P2(1)/c, a = 15.234(6) ?, b = 23.326(11) ?, c = 20.658(7) ?, beta = 102.46(3) degrees; V = 7,168(5) ?(3); Z = 4; R(F)() = 8.39%). Each W(2) unit is bridged by two cis cluster carboxylates, and the remaining four equatorial sites are occupied by monodentate [OOCCF(3)](-) ligands. The axial positions contain coordinated THF. The W(2) carboxylate is opened up (W-W distance of 2.449(2) ?) so that the free ends of the [OOCCF(3)](-) ligands on both W(2) carboxylate units can cooperate in chelating two Na(+) ions thereby forming a dimer of W(2) complexes. A distinctive EPR spectrum with g = 2.08 is consistent with each W(2) carboxylate being a mixed-valent W(II)-W(III) species. The reaction of W(2)(OOCCF(3))(4) with (CO)(9)Co(3)CCOOH in THF in the absence of Na[OOCCF(3)] leads to the expected diamagnetic W(II)-W(II) cluster carboxylate W(2){OOCCCo(3)(CO)(9)}(3)(OOCCF(3))(THF)(2), 3.     

Hypervalent organobismuth(iii) carbonate, chalcogenides and halides with the pendant arm ligands 2-(Me2NCH2)C6H4 and 2,6-(Me2NCH2)2C6H3

R2BiOH (1) [R = 2-(Me2NCH2)C6H4] and (R2Bi)2O (2) are formed by hydrolysis of R2BiCl with KOH. Single crystals of were obtained by air oxidation of (R2Bi)2. The reaction of R2BiCl and Na2CO3 leads to (R2Bi)2CO3 (3). 3 is also formed by the absorption of CO2 from the air in solutions of 1 or 2 in diethyl ether or toluene. (R2Bi)2S (4) is obtained from R2BiCl and Na2S or from (R2Bi)2 and S8. Exchange reactions between R2BiCl and KBr or NaI give R2BiX [X = Br (5), I (6)]. The reaction of RBiCl2 (7) with Na2S and [W(CO)5(THF)] gives cyclo-(RBiS)2[W(CO)5]2 (8). cyclo-(R'BiS)2 (9) [R' = 2,6-(Me2NCH2)2C6H3] is formed by reaction of R'BiCl2 and Na2S. The structures of were determined by single-crystal X-ray diffraction.     

Diazenide and hydrazide(2-) derivatives of the [Re(CO)3]+ core

Reaction of [ReBr3(CO)3]2- with aryldiazonium salts gives the Re(iii) diazenide complexes [ReBr2(NNC6H4R-4)(CO)2]-. The attachment of a PhNHCS tethering group to pyridyl hydrazine generates a HYNIC related proligand which gives a stable chelated pyridyliumthiocarbazide(2-) derivative of the [Re(I)(CO)3]+ core.     

Diastereospecific and diastereoselective syntheses of Ruthenium(II) complexes using N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N and their oxidation to imine ligands

Coordination of N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N 1 (Ar = 4-CH3-C6H4, 1a; 4-CH3O-C6H4, 1b; 2,6-(CH3)2-C6H3, 1c; 4-CF3-C6H4, 1d) to the moieties [Ru(bipy)2]2+, [Ru(eta5-C5H5)L]+ (L = CH3CN, CO), or [Ru(eta6-arene)Cl]2+ (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecific conditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondary amine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogen peroxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimental conditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatable amido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogen atoms in a beta position relative to the N-H bond. The structures of [Ru(2,2'-bipyridine)2(1b)](PF6)2, 2b; [Ru(2,2'-bipyridine)(2)(1c)](PF6)2, 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(eta6-C6H6)(1a)]PF6, 4a, have been confirmed by X-ray diffraction studies.     

Amine-amide equilibrium in gold(III) complexes and a gold(III)-gold(I) aurophilic bond

The ligands HN(CH2-2-C5H4N)2, BPMA, and PhCH2N(CH2-2-C5H4N)2, BBPMA, react with Na[AuCl4] to give the cationic complexes [AuCl(BPMA-H)]+ and [AuCl(BBPMA)]2+, respectively. The amido complex [AuCl(BPMA-H)]+ undergoes easy inversion at the amido nitrogen atom and can be reversibly protonated by triflic acid to give [AuCl(BPMA)]2+. The complex [AuCl(BBPMA)]2+ is easily decomposed in aqueous solution by cleavage of a carbon-nitrogen bond or, in dilute HCl solution, by protonation of the ligand to give [BBPMAH2]Cl[AuCl4] The complexes [BBPMAH2]Cl[AuCl4] and [BBPMAH2]Cl[AuCl2] can be formed by direct reaction of BBPMA with H[AuCl4]. Unusual forms of gold(III)...gold(III) and gold(III)...gold(I) aurophilic bonding are observed in the salts [AuCl(BPMA-H)][PF6] and [AuCl(BPMA-H)][AuCl2], respectively. The first comparison of the structures of gold(III) amine and amido complexes, in the cations [AuCl(BPMA-H)]+ and [AuCl(BPMA)]2+, indicates that there is little ppi-dpi bonding in the amido-gold bond and that the amide exerts a stronger trans influence than the amine group.     

Coordinatively and Electronically Unsaturated Tungsten(0) Carbonyl Complexes Stabilized by pi-Donating Amido Ligands

Novel, coordinatively and electronically unsaturated tungsten tricarbonyl dianions of 2-aminophenol and 1,2-diaminobenzene have been synthesized from the reaction of photogenerated W(CO)(5)THF and [Et(4)N][OC(6)H(4)NH(2)] with subsequent deprotonation by [Et(4)N][OH] accompanied by facile CO dissociation, and the reaction of W(CO)(5)THF and 2 equiv of [Et(4)N][NHC(6)H(4)NH(2)], respectively. These air-sensitive derivatives have been fully characterized both in solution (nu(CO) and (13)C NMR) and in the solid-state (X-ray crystallography). These metal dianions which have formally 16e(-) configurations are stabilized by pi-donation from the amido groups of the chelating ligands, as evident from short W-N bond distances. Both solution (nu(CO) and (13)C NMR) and solid-state (W-N vs W-O bond distances) data on these derivatives indicate the amido ligand to be a better pi-donor than the oxo ligand. Complex 2 crystallized in the monoclinic space group P2(1)/n with a = 14.499(5) ?, b = 14.708(5) ?, c = 15.137(4) ?, beta = 114.13(2) degrees, V = 2946(2) ?(3), and d(calc) = 1.433 g/cm(3), for Z = 4. Complex 3 crystallized in the triclinic space group P&onemacr; with a = 11.479(6) ?, b = 11.786(8) ?, c = 13.148(7) ?, alpha = 102.41(5) degrees, beta = 91.27(4) degrees, gamma = 99.96(5) degrees, V = 1708(2) ?(3), and d(calc) = 1.444 g/cm(3), for Z = 2.     

A simple approach to coordination compounds of the pentacyanocyclopentadienide anion

Deprotonation of [Et(3)NH][C(5)(CN)(5)] with metal bases provides a very simple approach to coordination compounds containing the pentacyanocyclopentadienide anion [C(5)(CN)(5)](-) (1). The three-dimensional polymer [Na(thf)(1.5)(1)](∞) and the molecular dimer [{(tmeda)(2)Na(1)}(2)] are obtained by reaction of this precursor with NaH in the presence of thf or tmeda (Me(2)NCH(2)CH(2)NMe(2)). Their single-crystal X-ray structures both reveal σ-bonded C≡N-Na arrangements and π stacking between [C(5)(CN)(5)](-) ions. DFT calculations on the [C(5)(CN)(5)](-) ion have been used to investigate the structures and bonding in [Na(thf)(1.5)(1)](∞) and [{(tmeda)(2)Na(1)}(2)]. The absence of π bonding of the metal ions in both complexes is due to dispersion of the negative charge from the C(5) ring unit to the C[triple chemical bond]N groups in the [C(5)(CN)(5)](-) ion, making the coordination chemistry of this anion distinctly different from that of cyclopentadienide C(5)H(5)(-).     

Two different hydrogen bond donor ligands together: a selectivity improvement in organometallic {Re(CO)3} anion hosts

Rhenium(I) compounds [Re(CO)(3)(Hdmpz)(2)(ampy)]BAr'(4) and [Re(CO)(3)(N-MeIm)(2)(ampy)]BAr'(4) (Hdmpz = 3,5-dimethylpyrazole, N-MeIm = N-methylimidazole, ampy = 2-aminopyridine or 3-aminopyridine) have been prepared stepwise as the sole reaction products in good yields. The cationic complexes feature two different types of hydrogen bond donor ligands, and their anion binding behavior has been studied both in solution and in the solid state. Compounds with 2-ampy ligands are labile in the presence of nearly all of the anions tested. The X-ray structure of the complex [Re(CO)(3)(Hdmpz)(2)(ampy)](+) (2) shows that the 2-ampy ligand is metal-coordinated through the amino group, a fact that can be responsible for its labile character. The 3-ampy derivatives (coordinated through the pyridinic nitrogen atom) are stable toward the addition of several anions and are more selective anion hosts than their tris(pyrazole) or tris(imidazole) counterparts. This selectivity is higher for compound [Re(CO)(3)(N-MeIm)(2)(MeNA)]BAr'(4) (5·BAr'(4), MeNA = N-methylnicotinamide) that features an amido moiety, which is a better hydrogen bond donor than the amino group. Some of the receptor-anion adducts have been characterized in the solid state by X-ray diffraction, showing that both types of hydrogen bond donor ligands of the cationic receptor participate in the interaction with the anion hosts. DFT calculations suggest that coordination of the ampy ligands is more favorable through the amino group only for the cationic complex 2, as a consequence of the existence of a strong intramolecular hydrogen bond. In all other cases, the pyridinic coordination is clearly favored.     

One-dimensional phosphinite platinum chains based on hydrogen bonding interactions and phosphinite tetranuclear platinum(II)-thallium(I) complexes

The mononuclear pentafluorophenyl platinum complex containing the chelated diphenylphosphinous acid/diphenylphosphinite system [Pt(C(6)F(5)){(PPh(2)O)(2)H}(PPh(2)OH)] 1 has been prepared and characterised. 1 and the related alkynyl complex [Pt(C[triple bond, length as m-dash]CBu(t)){(PPh(2)O)(2)H}(PPh(2)OH)] 2 form infinite one-dimensional chains in the solid state based on intermolecular O-H[dot dot dot]O hydrogen bonding interactions. Deprotonation reactions of [PtL{(PPh(2)O)(2)H}(PPh(2)OH)] (L = C(6)F(5), C[triple bond, length as m-dash]CBu(t), C[triple bond, length as m-dash]CPh 3) with [Tl(acac)] yields tetranuclear Pt(2)Tl(2) complexes [PtL{(PPh(2)O)(2)H}(PPh(2)O)Tl](2) (L = C(6)F(5) 4, C[triple bond, length as m-dash]CBu(t), C[triple bond, length as m-dash]CPh ). The structure of the tert-butylalkynyl derivative , established by X-ray diffraction, shows two anionic discrete units [Pt(C[triple bond, length as m-dash]CBu(t)){(PPh(2)O)(2)H}(PPh(2)O)](-) joined by two Tl(i) centres via Tl-O and Pt-Tl bonds. Despite the existence of Pt-Tl interactions, they do not show luminescence.     

Insertion of unsaturated organic electrophiles into molybdenumbond-alkoxide and rheniumbond-alkoxide bonds of neutral,stable carbonyl complexes

Alkoxo complexes [Re(OR)(CO)(3)(N-N)] (R=Me, Et, tBu; N-N=2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'bipyridine (bipy'), 1,10-phenanthroline (phen)) and [M(OMe)(eta(3)-allyl)(CO)(2)(phen)] (M=Mo, W) have been synthesized in good yields and using mild conditions by the reaction of sodium alkoxides with [Re(OTf)(CO)(3)(N-N)] and [MCl(eta(3)-allyl)(CO)(2)(phen)] precursors. These have been characterized by IR and NMR spectroscopy as well as by X-ray diffraction for [W(OMe)(eta(3)-allyl)(CO)(2)(phen)] (10). The reactions of the molybdenum and rhenium alkoxo complexes with isocyanates, R'NCO, yield [L(n)M[N(R')C(O)OR]] complexes; the carbamate ligand, which results from an R'NCO insertion into the Mbond;OR bond, is monodentate through the nitrogen atom. The solid-state structures of Mo and Re examples have been determined by X-ray diffraction. The geometry around the carbamate nitrogen of these compounds is planar, and the distances indicate delocalization of the nitrogen lone pair involving mainly the carbonyl groups. Experiments carried out with the Re complexes showed that aryl isocyanates are more reactive than their alkyl counterparts, and that bulky R' groups led to slow rates of insertion. Insertion reactions were also observed with isothiocyanates, although here it is the Sbond;C bond that inserts into the Mbond;OR bond, and the resulting ligand is bound to the metal by sulfur. Competition experiments with the Re compounds indicate that isocyanates are more reactive than isothiocyanates towards the Rebond;OR bonds. Tetracyanoethylene inserts into the Rebond;OMe bond of [Re(OMe)(CO)(3)(bipy')], forming a complex with a 2-methoxytetracyanoethyl ligand; the structure of which was determined by X-ray diffraction. The formation of the xanthato complex [Re(SC(S)OtBu)(CO)(3)(bipy)] (20) by reaction of [Re(OTf)(CO)(3)(bipy)] with CS(2) and NaOtBu, but not by the reaction of CS(2) and [Re(OtBu)(CO)(3)(bipy)] (5 a), suggests that the insertion reactions do not take place by ionization of the alkoxo complexes to give the free alkoxide ion.     

Trapping reactions of an intermediate containing a tungsten-phosphorus triple bond with alkynes

The thermolysis of the phosphinidene complex [Cp*P[W(CO)5]2] (1) in toluene in the presence of tBuC(triple bond)CMe leads to the four-membered ring complexes [[[eta2-C(Me)C(tBu)]Cp*(CO)W(mu3-P)[W(CO)3]][eta4:eta1:eta1-P[W(CO)5]WCp*(CO)C(Me)C(tBu)]] (4) as the major product and [[W[Cp*(CO)2]W(CO)2WCp*(CO)[eta1:eta1-C(Me)C(tBu)]](mu,eta3:eta2:eta1-P2[W(CO)5]] (5). The reaction of 1 with PhC(triple bond)CPh leads to [[W(Co)2[eta2-C(Ph)C(Ph)]][(eta4:eta1-P(W(CO)5]W[Cp*(CO)2)C(Ph)C(Ph)]] (6). The products 4 and 6 can be regarded as the formal cycloaddition products of the phosphido complex intermediate [Cp*(CO)2W(triple bond)P --> W(CO)5] (B), formed by Cp* migration within the phosphinidene complex 1. Furthermore, the reaction of 1 with PhC(triple bond)CPh gives the minor product [[[eta2:eta1-C(Ph)C(Ph)]2[W(CO)4]2][mu,eta1:eta1-P[C(Me)[C(Me)]3C(Me)][C(Ph)](C(Ph)]] (7) as a result of a 1,3-dipolaric cycloaddition of the alkyne into a phosphaallylic subunit of the Cp*P moiety of 1. Compounds 4-7 have been characterized by means of their spectroscopic data as well as by single-crystal X-ray structure analysis.     

Tetraaza analogues of lithium and sodium alums: synthesis and X-ray structures of the single strand polymer [Li(THF)2(Al[SO2(NtBu)2]2)] infinity and the contact ion pairs [Na(15-crown-5)][Al(SO2(NtBu)2)2] and ([Na(15-crown-5)][O2S(mu-NBn)2Al(mu-NBnSO2NBn)])2

The reaction of an alkali metal aluminohydride MAlH4 (M = Li, Na) with N,N'-bis-(tert-butyl)sulfamide or N,N'-bis-(benzyl)sulfamide in THF produces the complex ions (Al[SO2(NR)2]2)- (R = tBu, Bn). The X-ray structures of [Li(THF)2(Al[SO2(NtBu)2]2)] infinity (1), [Na(15-crown-5)][Al(SO2(NtBu)2)2], (2) and ([Na(15-crown-5)][O2S(mu-NBn)2Al(mu-NBnSO2NBn)])2 (3.3THF) are reported. The two diazasulfate ligands [SO2(NtBu)2]2- are N,N' chelated to Al3+ in both 1 and 2. In the lithium derivative 1 the spirocyclic (Al[SO2(NtBu)2]2)- anions are bridged by the bis-solvated cations Li(THF)2+ to give a polymeric strand. In the sodium salt 2 the complex anion is O,O' chelated to Na+, which is further encapsulated by a 15-crown-5 ligand to give a monomeric ion-pair complex. By contrast, the benzyl derivative 3 forms a dimer in which the terminal [SO2(NBn)2]2- ligands are (N,N'),(O,O') bis-chelated to Al3+ and Na+, respectively, and the bridging ligands adopt a novel N,O-chelate, N'-monodentate bonding mode. The central core of 3 consists of two four-membered AlOSN rings bridged by two NtBu groups. Crystal data: 1, orthorhombic, Pna2(1), a = 20.159(5) degrees, b = 10.354(3) degrees, c = 15.833(4) degrees, alpha = beta = gamma = 90 degrees, V = 3304.7(15) A3, Z = 4; 2, monoclinic, P2(1)/n, a = 16.031(2) A, b = 9.907(2) A, c = 23.963(4) A, beta = 103.326(2) degrees, Z = 4; 3, triclinic, P1, a = 12.7237(11) A, b = 14.0108(13) A, c = 16.2050(14) A, alpha = 110.351(2) degrees, beta = 111.538(2) degrees, gamma = 97.350(2) degrees, Z = 1.     

Synthesis and reactivity of the monomeric late-transition-metal parent amido complex [Ir(Cp*)(PMe3)(Ph)(NH2)

The late-transition-metal parent amido compound [Ir(Cp*)(PMe3)(Ph)(NH2)] (2) has been synthesized by deprotonation of the corresponding ammine complex [Ir(Cp*)(PMe3)(Ph)(NH3)][OTf] (6) with KN(SiMe3)2. An X-ray structure determination has ascertained its monomeric nature. Proton-transfer studies indicate that 2 can successfully deprotonate p-nitrophenylacetonitrile, aniline, and phenol. Crystallographic analysis has revealed that the ion pair [Ir(Cp*)(PMe3)(Ph)(NH3)][OPh] (8) exists as a hydrogen-bonded dimer in the solid state. Reactions of 2 with isocyanates and carbodiimides lead to overall insertion of the heterocumulenes into the N--H bond of the Ir-bonded amido group, demonstrating the ability of 2 to act as an efficient nucleophile. Intriguing reactivity is observed when amide 2 reacts with CO or 2,6-dimethylphenyl isocyanide. eta4-Tetramethylfulvene complexes [Ir(eta4-C5Me4CH2)(PMe3)(Ph)(L)] (L=CO (15), CNC6H3-2,6-(CH3)2 (16)) are formed in solution through displacement of the amido group by the incoming ligand followed by deprotonation of a methyl group on the Cp* ring and liberation of ammonia. Conclusive evidence for the presence of the Ir-bonded eta4-tetramethylfulvene moiety in the solid state has been provided by an X-ray diffraction study of complex 16.     

Novel dimetal bridging carbene complexes derived from a terminal carbonyl dimetal compound. Syntheses, structures and reactivities of 7H-indene-coordinated diiron bridging carbene complexes

Pentacarbonyl-7H-indenediiron, [Fe2(CO)5(eta3,eta5-C9H8)] (1), reacts with aryllithium, ArLi (Ar = C6H5, p-C6H5C6H4), followed by alkylation with Et3OBF4 to give novel 7H-indene-coordinated diiron bridging alkoxycarbene complexes [Fe2{mu-C(OC2H5)Ar}(CO)4(eta4,eta4-C9H8)] (2, Ar = C6H5; 3, Ar = p-C6H5C6H4). Complexes 2 and 3 react with HBF4.Et2O at low temperature to yield cationic bridging carbyne complexes [Fe2(mu-CAr)(CO)4(eta4,eta4-C9H8)]BF4 (4, Ar = C6H5; 5, Ar = p-C6H5C6H4). Cationic 4 and 5 react with NaBH4 in THF at low temperature to afford diiron bridging arylcarbene complexes [Fe2{mu-C(H)Ar}(CO)4(eta4,eta4-C9H8)] (6, Ar = C6H5; 7, Ar = p-C6H5C6H4). The similar reactions of 4 and 5 with NaSC6H4CH3-p produce the bridging arylthiocarbene complexes [Fe2{mu-C(Ar)SC6H4CH3-p}(CO)4(eta4,eta4-C9H8)] (8, Ar = C6H5; 9, Ar = p-C6H5C6H4). Cationic 4 and 5 can also react with anionic carbonylmetal compounds Na[M(CO)5(CN)] (M = Cr, Mo, W) to give the diiron bridging aryl(pentacarbonylcyanometal)carbene complexes [Fe2{mu-C(Ar)NCM(CO)5}(CO)4(eta4,eta4-C9H8)] (10, Ar = C6H5, M = Cr; 11, Ar = p-C6H5C6H4, M = Cr; 12, Ar = C6H5, M = Mo; 13, Ar = p-C6H5C6H4, M = Mo; 14, Ar = C6H5, M = W; 15, Ar = p-C6H5C6H4, M = W). Interestingly, in CH2Cl2 solution at room temperature complexes 10-15 were transformed into the isomerized 7H-indene-coordinated monoiron complexes [Fe(CO)2(eta5-C9H8)C(Ar)NCM(CO)5] (16, Ar = C6H5, M = Cr; 17, Ar = p-C6H5C6H4, M = Cr; 18, Ar = C6H5, M = Mo; 19, Ar = p-C6H5C6H4, M = Mo; 20, Ar = C6H5, M = W; 21, Ar = p-C6H5C6H4, M = W), while complex 3 was converted into a novel ring addition product [Fe2{C(OC2H5)C6H4C6H5-p-(eta2,eta5-C9H8)}(CO)5] (22) under the same conditions. The structures of complexes 2, 6, 8, 14, 18 and 22 have been established by X-ray diffraction studies.     

Cobalt(III) carbonate and bicarbonate chelate complexes of tripodal tetraamine ligands containing pyridyl donors: the steric basis for the stability of chelated bicarbonate complexes

The synthesis and characterization (X-ray crystallography, UV/vis spectroscopy, electrochemistry, ESI-MS, and (1)H, (13)C, and (59)Co NMR) of the complexes [Co(L)(O(2)CO)]ClO(4)xH(2)O (L = tpa (tpa = tris(2-pyridylmethyl)amine) (x = 1), pmea (pmea = bis((2-pyridyl)methyl)-2-((2-pyridyl)ethyl)amine) (x = 0), pmap (pmap = bis(2-(2-pyridyl)ethyl)(2-pyridylmethyl)amine) (x = 0), tepa (tepa = tris(2-(2-pyridyl)ethyl)amine) (x = 0)) which contain tripodal tetradentate pyridyl ligands and chelated carbonate ligands are reported. The complexes display different colors in both the solid state and solution, which can be rationalized in terms of the different ligand fields exerted by the tripodal ligands. Electrochemical data show that [Co(tepa)(O(2)CO)](+) is the easiest of the four complexes to reduce, and the variation in E(red.) values across the series of complexes can also be explained in terms of the different ligand fields exerted by the tripodal ligands, as can the (59)Co NMR data which show a chemical shift range of over 2000 ppm for the four complexes. [Co(pmea)(O(2)CO)](+) is fluxional in aqueous solution, and VT NMR spectroscopy ((1)H and (13)C) in DMF-d(7) (DMF = dimethylformamide) over the temperature range -25.0 to 75.0 degrees C are consistent with inversion of the unique six-membered chelate ring. This process shows a substantial activation barrier (DeltaG(#) = 58 kJ mol(-1)). The crystal structures of [Co(tpa)(O(2)CO)]ClO(4)xH(2)O, [Co(pmea)(O(2)CO)]ClO(4).3H(2)O, [Co(pmap)(O(2)CO)]ClO(4), and [Co(tepa)(O(2)CO)]ClO(4) are reported, and the complexes containing the asymmetric tripodal ligands pmea and pmap both crystallize as the 6-isomer. The carbonate complexes all show remarkable stability in 6 M HCl solution, with [Co(pmap)(O(2)CO)](+) showing essentially no change in its UV/vis spectrum over 4 h in this medium. The chelated bicarbonate complexes [Co(pmea)(O(2)COH)]ZnCl(4), [Co(pmap)(O(2)COH)][Co(pmap)(O(2)CO)](ClO(4))(3), [Co(pmap)(O(2)COH)]ZnCl(4)xH(2)O, and [Co(pmap(O(2)COH)]ZnBr(4)x2H(2)O can be isolated from acidic aqueous solution, and the crystal structure of [Co(pmap)(O(2)COH)]ZnCl(4)x3H(2)O is reported. The stability of the carbonate complexes in acid is explained by analysis of the crystallographic data for these, and other slow to hydrolyze chelated carbonate complexes, which show that the endo (coordinated) oxygen atoms are significantly hindered by atoms on the ancillary ligands, in contrast to complexes such as [Co(L)(O(2)CO)](+) (L = (NH(3))(4), (en)(2), tren, and nta), which undergo rapid acid hydrolysis and which show no such steric hindrance.