Reactivity of [RuHCl(PiPr3)2]2 with functionalized vinyl substrates. The H2 ligand as a sensitive probe of electronic structure.

Reaction of [RuHClL2]2 (L = PiPr3) with 2-vinylpyridine gives L2ClRu(eta 2-CH=CHC5H4N) with liberation of H2. Reaction of [RuHClL2]2 with a range of olefins D(H)C=CR(EWG) substituted by electron-donating (D) and -withdrawing (EWG) groups occurs by oxidative addition of a vinyl C-H bond to give the metallacycles L2ClHnRu(eta 2-(++)C(D)=CR(EWG)). The 13C chemical shift of ++C and the fate of the "Hn" unit (decoordination, binding as H2, or binding as two hydrides) are strongly correlated, depend on the donating and withdrawing power of D and EWG, and can be used to decide whether ++C binds to Ru as a carbene or as a vinyl. These results emphasize the reducing power of Ru(II) when pi-acid ligands such as CO are absent.

Influence of the [2.1.1]-(2,6)-pyridinophane macrocycle ring size constraint on the structure and reactivity of copper complexes.

The macrocycle [2.1.1]-(2,6)-pyridinophane (L) binds to CuCl to give a monomeric molecule with tridentate binding of the ligand but in a distorted tetrahedral "3 + 1" geometry, where one nitrogen forms a longer (by 0.12 A) bond to Cu. In dichloromethane solvent this pyridine donor undergoes facile site exchange with a second pyridine in the macrocycle, to give time-averaged mirror symmetry. Both experimental and density functional theory studies of the product of chloride abstraction, using NaBAr(F)(4) in CH(2)Cl(2), show that the Cu(+) binds in a trigonal pyramidal, not planar, arrangement in LCu(+). This illustrates the ability of macrocyclic ligand constraint to impose an electronically unfavorable geometry on 3-coordinate Cu(I). LCuBAr(F)(4) and a triflate analogue LCu(I)(OTf) readily react with oxygen in dichloromethane to produce, in the latter case, a hydroxo-bridged dimer [LCu(II)(micro-OH)](2)(OTf)(2), of the intact (unoxidized) ligand L. Since the analogous LCuCl does not react as fast with O(2) in CH(2)Cl(2), outer-sphere electron transfer is concluded to be ineffective for oxidation of cuprous ion here.

New approach to Ru(II) pincer ligand chemistry. Bis(tert-butylaminomethyl)pyridine coordinated to ruthenium(II).

Reaction of 2,6-bis-(tBuNHCH2)2NC5H3 ("N2py") with RuCl2(PPh3)3 gives two isomers of Ru(N2py)Cl2(PPh3), 5, while reaction with RuCl2(DMSO)4 (DMSO = Me2SO) gives isomerically pure Ru(N2py)Cl2(DMSO), whose structure is reported. The PPh3 of 5 can be replaced by CO, P(OPh)3, or pyridine. The chlorides in Ru(N2py)Cl2(CO) can both be replaced by F3CSO3-. Isomer structure preferences are discussed, and the reaction of Ru(N2py)Cl2(pyridine) with O2 gives apparent oxidation of N2py to give the diimine.

C-D(0) (D(0) = pi-donor, F) Cleavage in H(2)C=CH(D(0)) by (Cp(2)ZrHCl)(n): mechanism, agostic fluorines, and a carbene of Zr(IV).

Consistent with the C-O cleavage behavior of vinyl ethers, vinyl fluoride reacts with Cp(2)ZrHCl to give Cp(2)ZrFCl and C(2)H(4) as primary products. DFT (B3PW91) calculations show this reaction to be highly exoenergetic (-55 kcal/mol), and reveal a sigma-bond metathesis mechanism to be unfavorable compared to a Zr-H addition across the C=C bond, with regiochemistry placing F on C(beta) of the resulting fluoroethyl ligand. beta-F elimination (onto Zr) then completes the reaction. There is no eta(2)-olefin intermediate on the reaction path. DFT calculations seeking the energy and structure of the two carbenes Cp(2)ZrHCl[CF(CH(3))] and Cp(2)ZrFCl[CH(CH(3))] are also described.

Metal clusters in catalysis: Hydrocarbon reactions.

A set of metal carbonyl clusters, Ru(3)(CO)(12), Os(3)(CO)(12), and Ir(4)(CO)(12), has been evaluated as catalysts for a series of hydrocarbon reactions which comprise skeletal rearrangement, metathesis, dehydrogenation, hydrogenation, isomerization, and H-D exchange. None was especially effective as a hydrogenation catalyst even for olefins. Os(3)(CO)(12) was a catalyst for H-D exchange between C(6)H(6) and D(2) at 195 degrees but the ruthenium congener was inactive at temperatures below 175 degrees , a temperature where ruthenium metal formed at an appreciable rate. Deuterium incorporation in the benzene was a single-step process. Ir(4)(CO)(12) was an effective catalyst for the conversion of cyclohexadiene to cyclohexene and benzene. A similar reaction occurred with cyclohexene but the rate was extremely low at 160 degrees . The ruthenium and osmium clusters catalyzed the isomerization of linear hexenes, with the former the more active. Relative rates for the hexenes were 1 > 2 > 3. At high temperatures, the osmium and iridium clusters catalyzed skeletal reactions of 2-hexene, as evidenced by the formation of pentenes, heptenes, heptanes, and small amounts of propane.

A new class of electron-rich unsaturated molecules: Ru2HnX4-n(PiPr3)4, X = anion.

Synthesis, spectroscopic, and X-ray structural characterization of Ru2HnCl4-nL4 (n = 2, 3) and Ru2H2F2L4 (L = PiPr3) are reported. The structure of Ru2HCl3L4 is also reported. These are dinuclear species containing two five-coordinate, approximately square-pyramidal metal atoms. Halides, not hydrides, preferentially occupy bridging sites, and the RuXL2 terminal moiety shows limited fluxionality, but hydrides do not migrate between metals. The limited steric protection provided by PiPr3 is evident from the dimerization observed and from the fact that all these structures have rather small [symbol: see text]P-Ru-P (approximately 105 degrees). Also reported are RuHXL2 species with X = acetylacetonate, phenoxide, O3SCH3, and O3SCF3. Several examples of coordinated olefin to complexed carbene conversions are used to test the influence of anion X on reactivity.

Unsaturated Ru(0) species with a constrained bis-phosphine ligand: [Ru(CO)2(tBu2PCH2CH2PtBu2)]2. Comparison to [Ru(CO)2(PtBu2Me)2].

The synthesis of Ru(C2H4)(CO)2(dtbpe) (dtbpe = tBu2PC2H4PtBu2), then green [Ru(CO)2(dtbpe)]n is described. In solution, n = 1, while in the solid state, n = 2; the dimer has two carbonyl bridges. DFTPW91, MP2, and CCSD(T) calculations show that the potential energy surface for bending one carbonyl out of the RuP2C(O) plane is essentially flat. Ru(CO)2(dtbpe) reacts rapidly in benzene solution to oxidatively add the H-E bond of H2, HCl, HCCR (R = H, Ph), [HOEt2]BF4, and HSiEt3. The H-C bond of C6HF5 oxidatively adds at 80 degrees C. CO adds, as does the C=C bond of H2C=CHX (X = H, F, Me). The following do not add: N2, THF, acetone, H3COH, and H2O.

Structural distortions in mer-M(H)3(NO)L2 (M = Ru, Os) and their influence on intramolecular fluxionality and quantum exchange coupling.

Molecules of the type mer-M(H)3(NO)L2 [M = Ru (1), Os (2); L = PR3] are characterized on the basis of 1H NMR T1min values and IR spectra as pseudo-octahedral trihydrides significantly distorted by compression of the cis H-M-H angles to approximately 75 degrees. The distortion, uncharacteristic of six-coordinate d6 complexes, is rationalized with DFT (B3LYP) calculations as being driven by increased H-to-M sigma donation and by the exceptional pi-accepting ability of linear NO+. In both 1 and 2, hydrides undergo intramolecular site exchange with delta HHH++(1) = 10-11 kcal/mol and delta HHH++(2) = 16-20 kcal/mol, depending on L, whereas for mer-Ru(H)3(NO)(PtBu2Me)2 (1b), moderate exchange couplings (up to 77 Hz) are featured in the low-temperature 1H NMR spectra, in addition to chemical exchange. On the basis of experimental and theoretical results, a dihydrogen intermediate is suggested to mediate hydride site exchange in 1. The cis H-M-H distortion shortens the tunneling path for the exchanging hydrides in 1, thereby increasing the tunneling rate; diminishes the "conflict" between trans hydrides in the mer geometry; and decreases the nucleophilicity of the hydrides. The generality of the observed structural distortion and its dependence on the ligand environment in late transition metal tri- and dihydrides are discussed. A less reducing metal center is generally characterized by greater distortion.

Facile C(sp(2))/OR bond cleavage by Ru or Os.

Os(H)(3)ClL(2) (L = P(i)Pr(3) or P(t)Bu(2)Me) are shown to be useful "precursors" to "OsHClL(2)", which react with vinyl ethers to form first an eta(2)-olefin adduct and then isomerize to the carbenes, OsHCl[CMe(OR)]L(2). Subsequent R- and L-dependent reactions involve C(sp(2))-OR bond cleavage, to make either carbyne or vinylidene complexes. The mechanisms of these reactions are explored, and the thermodynamic disparity of Ru versus Os and the influence of the OR group and the spectator phosphine ligands are discussed based on DFT (B3PW91) calculations.

Effect of Lewis acidity on the synthesis of RuHCl(CO)(phosphine)(2): subtle influence of steric and electronic effects among P(i)Pr(3), P(i)Pr(2)(3,5-(CF(3))(2)C(6)H(3)), and P(i)Pr(2)Me.

To evaluate the influence of steric, electronic, and synthetic factors, the synthesis of RuHCl(CO)[P(i)Pr(2)(3,5-(CF(3))(2)C(6)H(3))](2) was carried out, and its Lewis acidity toward Cl- was compared to that of RuHCl(CO)(P(i)Pr(3))(2). In this synthesis, Na(2)CO(3) was shown to be a more effective base than NEt(3), because Na+ can better mask the nucleophilicity of the potential ligand Cl-. An X-ray structure determination of the hydride-free species RuCl(2)(CO)(P(i)Pr(2)Me)(2) shows it to be a dimer, and this solid-state structure persists in solution, but as several different isomers. The synthesis of RuHCl(CO)(P(i)Pr(2)Me)(3) shows that three of this smaller phosphine can crowd around Ru, but dynamic NMR spectra show one phosphine to be weakly bound. The rate of reaction of Me(3)SiC(triple bond)CH with this molecule is suppressed by added free P(i)Pr(2)Me, indicating phosphine dissociation to be a mechanistic component.