Structural diversity in a family of copper(I) thioether complexes

Copper(I) complexes of the tridentate thioether ligands [PhB(CH(2)SCH(3))(3)] (abbreviated PhTt), [PhB(CH(2)SPh)(3)] (PhTt(Ph)), [PhB(CH(2)S(t)()Bu)(3)] (PhTt(t)()(Bu)), and [PhB(CH(2)S(p)()Tol)(3)] (PhTt(p)()(Tol)) and bidentate thioether ligands [Ph(2)B(CH(2)SCH(3))(2)] (Ph(2)Bt), [Et(2)B(CH(2)SCH(3))(2)] (Et(2)Bt), and [Ph(2)B(CH(2)SPh)(2)] (Ph(2)Bt(Ph)) have been prepared and characterized. The solution and solid state structures are highly sensitive to the identity of the borato ligand employed. Ligands possessing the smaller (methylthio)methyl donors, [PhTt] and [Ph(2)Bt], yielded tetrameric species, [(PhTt)Cu](4) and [(Ph(2)Bt)Cu](4), containing both terminal and bridging thioether ligation. The ligands containing the larger (arylthio)methyl groups, [PhTt(Ph)] and [PhTt(p)()(Tol)], form monomeric [PhTt(Ar)]Cu(NCCH(3)) in solution and one-dimensional extended structures in the solid state. Each complex type reacted cleanly with acetonitrile, pyridine, or triphenylphosphine generating the corresponding four-coordinate monomer, of which [PhTt(Ph)]Cu(PPh(3)), [PhTt(p)()(Tol)]Cu(PPh(3)), and [Et(2)Bt]Cu(PPh(3))(2) have been structurally characterized.     

Do S,S'-coordinated o-dithiobenzosemiquinonate(1-) radicals exist in coordination compounds? the [AuIII(1,2-C6H4S2)2]1 -/0 couple

The square planar, light-green, diamagnetic complex [N(n-Bu)(4)][Au(III)(L(t)()(-)(Bu))(2)] (1) reacts with iodine in acetone affording the neutral paramagnetic species [Au(L(t)()(-)(Bu))(2)] (1a) (S = (1)/(2)) where H(2)[L(t)()(-)(Bu)] represents the ligand 3,5-di-tert-butyl-1,2-benzenedithiol. The corresponding complexes containing the unsubstituted ligand H(2)[L], 1,2-benzenedithiol, namely [N(n-Bu)(3)H][Au(L)(2)] (2) and [Au(L)(2)] (2a), have also been prepared and characterized by X-ray crystallography; the structure of the latter has been reported in ref 10. (197)Au M?ssbauer spectra of 1 and 1a clearly show that the one-electron oxidation is ligand-centered and does not involve the formation of Au(IV) (d(7)). The spectroscopic features of the ligand mixed-valent species 1a were determined by UV-vis, EPR, and IR spectroscopy which allows the detection of S,S-coordinated 1,2-dithiobenzosemiquinonate(1-) radicals in coordination compounds.     

Spectroscopic study of [Fe2O2(5-Et3-TPA)2]3+: nature of the Fe2O2 diamond core and its possible relevance to high-valent binuclear non-heme enzyme intermediates

The spectroscopic properties and electronic structure of an Fe(2)(III,IV) bis-mu-oxo complex, [Fe(2)O(2)(5-Et(3)-TPA)(2)](ClO(4))(3) where 5-Et(3)-TPA = tris(5-ethyl-2-pyridylmethyl)amine, are explored to determine the molecular origins of the unique electronic and geometric features of the Fe(2)O(2) diamond core. Low-temperature magnetic circular dichroism (MCD) allows the two features in the broad absorption envelope (4000-30000 cm(-)(1)) to be resolved into 13 transitions. Their C/D ratios and transition polarizations from variable temperature-variable field MCD saturation behavior indicate that these divide into three types of electronic transitions; t(2) --> t(2) involving excitations between metal-based orbitals with pi Fe-O overlap (4000-10000 cm(-)(1)), t(2)/t(2) --> e involving excitations to metal-based orbitals with sigma Fe-O overlap (12500-17000 cm(-)(1)) and LMCT (17000-30000 cm(-)(1)) and allows transition assignments and calibration of density functional calculations. Resonance Raman profiles show the C(2)(h)() geometric distortion of the Fe(2)O(2) core results in different stretching force constants for adjacent Fe-O bonds (k(str)(Fe-O(long)) = 1.66 and k(str)(Fe-O(short)) = 2.72 mdyn/A) and a small ( approximately 20%) difference in bond strength between adjacent Fe-O bonds. The three singly occupied pi-metal-based orbitals form strong superexchange pathways which lead to the valence delocalization and the S = (3)/(2) ground state. These orbitals are key to the observed reactivity of this complex as they overlap with the substrate C-H bonding orbital in the best trajectory for hydrogen atom abstraction. The electronic structure implications of these results for the high-valent enzyme intermediates X and Q are discussed.     

New synthetic routes to a disulfidodinickel(II) complex: characterization and reactivity of a Ni2(mu-eta2:eta2-S2) core

Activation of elemental sulfur by the monovalent nickel complex [PhTt (tBu)]Ni(CO) [PhTt(tBu)=phenyl{tris[(tert-butylmethyl)thio]methyl}borate] generates the disulfidodinickel(II) complex 2. This species is alternatively accessible via thermal decomposition of [PhTt (tBu)]Ni(SCPh3). Spectroscopic, magnetic, and X-ray diffraction studies establish that 2 contains a mu-eta(2):eta(2)-S2 ligand that fosters antiferromagnetic exchange coupling between the Ni (II) ions. This observation is in contrast to the lighter congener, oxygen, which strongly favors the bis(mu-oxo)dinickel(III) structure. 2 oxidizes PPh 3 to SPPh3 and reacts with O2, generating several products, one of which has been identified as [(PhTt (tBu))Ni]2(mu-S) (3).     

Formation and characterization of the hexanuclear platinum cluster [Pt6(mu-PBu(t)2)4(CO)6](CF3SO3)2 through structural, electrochemical, and computational analyses

The reaction between equimolar amounts of Pt(3)(mu-PBu(t)()(2))(3)(H)(CO)(2), Pt(3)()H, and CF(3)SO(3)H under CO atmosphere affords the triangular species [Pt(3)(mu-PBu(t)()(2))(3)(CO)(3)]X, [Pt(3)()(CO)(3)()(+)()]X (X = CF(3)SO(3)(-)), characterized by X-ray crystallography, or in an excess of acid, [Pt(6)(mu-PBu(t)()(2))(4)(CO)(6)]X(2), [Pt(6)()(2+)()]X(2)(). Structural determination shows the latter to be a rare hexanuclear cluster with a Pt(4) tetrahedral core formed by joining the unbridged sides of two orthogonal Pt(3) triangles. The dication Pt(6)()(2+)() features also extensive redox properties as it undergoes two reversible one-electron reductions to the congeners [Pt(6)(mu-PBu(t)()(2))(4)(CO)(6)](+) (Pt(6)()(+)(), E(1/2) = -0.27 V) and Pt(6)(mu-PBu(t)()(2))(4)(CO)(6) (Pt(6)(), E(1/2) = -0.54 V) and a further quasi-reversible two-electron reduction to the unstable dianion Pt(6)()(2)()(-)() (E(1/2) = -1.72 V). The stable radical (Pt(6)()(+)()) and diamagnetic (Pt(6)()) species are also formed via chemical methods by using 1 or 2 equiv of Cp(2)Co, respectively; further reduction of Pt(6)()(2+)() causes fast decomposition. The chloride derivatives [Pt(6)(mu-PBu(t)()(2))(4)(CO)(5)Cl]X, (Pt(6)()Cl(+)())X, and Pt(6)(mu-PBu(t)()(2))(4)(CO)(4)Cl(2), Pt(6)()Cl(2)(), observed as side-products in some electrochemical experiments, were prepared independently. The reaction leading to Pt(3)()(CO)(3)()(+)() has been analyzed with DFT methods, and identification of key intermediates allows outlining the reaction mechanism. Moreover, calculations for the whole series Pt(6)()(2+)() --> Pt(6)()(2)()(-)()( )()afford the otherwise unknown structures of the reduced derivatives. While the primary geometry is maintained by increasing electron population, the system undergoes progressive and concerted out-of-plane rotation of the four phosphido bridges (from D(2)(d)() to D(2) symmetry). The bonding at the central Pt(4) tetrahedron of the hexanuclear clusters (an example of 4c-2e(-) inorganic tetrahedral aromaticity in Pt(6)()(2+)()) is explained in simple MO terms.     

Reaction properties of the trans-hyponitrite complex [Ru2(CO)4(mu-H)(mu-PBu(t)2)(mu-Ph2PCH2PPh2)(mu-eta2-ONNO)

The protonation of [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNO)] (1) with HBF(4) occurs at the oxygen of the noncoordinating side of the trans-hyponitrite ligand to give [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNOH)][BF(4)] (2) in good yield. The monoprotonated hyponitrite in 2 is deprotonated easily by strong bases to regenerate 1. Furthermore, 1 reacts with the methylating reagent [Me(3)O][BF(4)] to afford [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNOMe)][BF(4)] (3). The molecular structures of 2 and 3 have been determined crystallographically, and the structure of 2 is discussed with the results of the DFT/B3LYP calculations on the model complex [Ru(2)(CO)(4)(mu-H)(mu-PH(2))(mu-H(2)PCH(2)PH(2))(mu-eta(2)-ONNOH)](+) (2a). Moreover, the thermolysis of 2 in ethanol affords [Ru(2)(CO)(4)(mu-H)(mu-OH)(mu-PBu(t)()(2))(mu-dppm)][BF(4)] (4) in high yield, and the deprotonation of 4 by DBU in THF yields the novel complex [Ru(2)(CO)(4)(mu-OH)(mu-PBu(t)()(2))(mu-dppm)] (5).     

Palladium-catalyzed formylation of aryl bromides: elucidation of the catalytic cycle of an industrially applied coupling reaction

The first comprehensive study of the catalytic cycle of the palladium-catalyzed formylation of aryl bromides with synthesis gas (CO/H2, 1:1) is presented. The formylation in the presence of efficient (Pd/PR2(n)Bu, R = 1-Ad, (t)Bu) and nonefficient (Pd/P(t)Bu3) catalysts was investigated. The main organometallic complexes involved in the catalytic cycle were synthesized and characterized, and their solution chemistry was studied in detail. Comparison of stoichiometric and catalytic reactions using P(1-Ad)2(n)Bu, the most efficient ligand known for the formylation of aryl halides, led to two pivotal results: (1) The corresponding carbonylpalladium(0) complex [Pd(n)(CO)(m)L(n)] and the respective hydrobromide complex [Pd(Br)(H)L2] are resting states of the active catalyst, and they are not directly involved in the catalytic cycle. These complexes maintain the concentration of most active [PdL] species at a low level throughout the reaction, making oxidative addition the rate-determining step, and provide high catalyst longevity. (2) The product-forming step proceeds via base-mediated hydrogenolysis of the corresponding acyl complex, e.g., [Pd(Br)(p-CF3C6H4CO){P(1-Ad)2(n)Bu}]2 (8), under mild conditions (25-50 degrees C, 5 bar). Stoichiometric studies using the less efficient Pd/P(t)Bu3 catalyst resulted in the isolation and characterization of the first stable three-coordinated neutral acylpalladium complex, [Pd(Br)(p-CF3C6H4CO)(P(t)Bu3)] (10). Hydrogenolysis of 10 needed significantly more drastic conditions compared to that of dimeric 8. In the presence of amine base, complex 10 gave a catalytically inactive diamino acyl complex, which explains the low activity of the Pd/P(t)Bu3 catalyst formylation of aryl bromides.     

Monovalent iron in a sulfur-rich environment

A series of low-coordinate, paramagnetic iron complexes in a tris(thioether) ligand environment have been prepared. Reduction of ferrous {[PhTt(tBu)]FeCl}2 [1; PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate] with KC8 in the presence of PR3(R = Me or Et) yields the high-spin, monovalent iron phosphine complexes [PhTt(tBu)]Fe(PR3) (2). These complexes provide entry into other low-valent derivatives via ligand substitution. Carbonylation led to smooth formation of the low-spin dicarbonyl [PhTt(tBu)]Fe(CO)2 (3). Alternatively, replacement of PR 3 with diphenylacetylene produced the high-spin alkyne complex [PhTt(tBu)]Fe(PhCCPh) (4). Lastly, 2 equiv of adamantyl azide undergoes a 3 + 2 cycloaddition at 2, yielding high-spin dialkyltetraazadiene complex 5.     

Coordination of diatomic ligands to heme: simply CO

The synthesis and molecular structures of three iron(II) porphyrinates with only CO as the axial ligand(s) are reported. Two five-coordinate [Fe(OEP)(CO)] derivatives have Fe-C = 1.7077(13) and 1.7140(10) A, much shorter than those of six-coordinate [Fe(OEP)(Im)(CO)], although nu(C-O) is 1944-1948 cm(-1). The six-coordinate species [Fe(OEP)(CO)2] has also been studied. The competition for pi-back-bonding of two CO ligands leads to Fe-C distance of 1.8558(10) A and nu(C-O) being increased to 2021 cm(-1). The M?ssbauer spectrum has a quadrupole splitting constant of 0 mm/s at 4.2 K, indicating high electronic symmetry.     

Steric and electronic properties of N-heterocyclic carbenes (NHC): a detailed study on their interaction with Ni(CO)4

N-heterocyclic carbene ligands IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5) react with Ni(CO)(4) to give the saturated tricarbonyl complexes Ni(CO)(3)(IMes) (8), Ni(CO)(3)(SIMes) (9), Ni(CO)(3)(IPr) (10), Ni(CO)(3)(SIPr) (11), and Ni(CO)(3)(ICy) (12), respectively. The electronic properties of these complexes have been compared to their phosphine analogues of general formula Ni(CO)(3)(PR(3)) by recording their nu(CO) stretching frequencies. While all of these NHCs are better donors than tertiary phosphines, the differences in donor properties between ligands 1-5 are surprisingly small. Novel, unsaturated Ni(CO)(2)(IAd) (13) and Ni(CO)(2)(I(t)()Bu) (14) compounds are obtained from the reaction of Ni(CO)(4) with IAd (6) and I(t)()Bu (7). Complexes 13 and 14 are highly active toward substitution of the NHC as well as the carbonyl ligands. This has allowed the determination of Ni-C(NHC) bond dissociation energies and the synthesis of various unsaturated Ni(0) and Ni(II) complexes. Computational studies on compounds 8-14 are in line with the experimental findings and show that IAd (6) and I(t)()Bu (7) are more bulky than IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5). Furthermore, a method based on %V(bur) values has been developed for the direct comparison of steric requirements of NHCs and tertiary phosphines. Complexes 8-14, as well as NiCl(C(3)H(5))(I(t)()Bu) (16) and NiBr(C(3)H(5))(I(t)()Bu) (17), have been characterized by X-ray crystallography.     

Nickel complexes of bidentate [S2] and [SN] borato ligands

Nickel(II) complexes of the monoanionic borato ligands [Ph2B(CH2SCH3)2] (abbreviated Ph2Bt), [Ph2B(CH2S(t)Bu)2] (Ph2Bt(tBu)), [Ph2B(1-pyrazolyl)(CH2SCH3)], and [Ph2B(1-pyrazolyl)(CH2S(t)Bu)] have been prepared and characterized. While [Ph2Bt] formed the square planar homoleptic complex, [Ph2Bt]2Ni, the larger [S2] ligand with tert-butyl substituents, [Ph2BttBu], yielded an unexpected organometallic derivative, [Ph2Bt(tBu)]Ni(eta2-CH2SBut), resulting from B-C bond rupture. The analogous thiametallacycle derived from the [S3] ligand, [PhB(CH2S(t)Bu)3] (PhTt(tBu)), has been structurally authenticated (Schebler, P. J.; Mandimutsira, B. S.; Riordan, C. G.; Liable-Sands, L.; Incarvito, C. D.; Rheingold, A. L. J. Am. Chem. Soc. 2001, 123, 331). The [SN] borato ligands formed exclusively the cis stereoisomers upon reaction with Ni(II) sources, [Ph2B(1-pyrazolyl)(CH2SR)]2Ni. Analysis of the Ni(II/I) reduction potentials by cyclic voltammetry revealed a approximately 600 mV anodic shift upon replacement of two thioether donors ([Ph2Bt]2Ni) with two pyrazolyl donors ([Ph2B(1-pyrazolyl)(CH2SCH3)]2Ni) consistent with the all thioether environment stabilizing the lower oxidation state of nickel.     

Three-coordinate NiII: tracing the origin of an unusual, facile Si-C(sp3) bond cleavage in [(tBu2PCH2SiMe2)2N]Ni+

All attempts to synthesize (PNP)Ni(OTf) form instead ((t)Bu(2)PCH(2)SiMe(2)NSiMe(2)OTf)Ni(CH(2)P(t)Bu(2)). Abstraction of F(-) from (PNP)NiF by even a catalytic amount of BF(3) causes rearrangement of the (transient) (PNP)Ni(+) to analogous ring-opened [((t)Bu(2)PCH(2)SiMe(2)NSiMe(2)F)]Ni(CH(2)P(t)Bu(2)). Abstraction of Cl(-) from (PNP)NiCl with NaB(C(6)H(3)(CF(3))(2))(4) in CH(2)Cl(2) or C(6)H(5)F gives (PNP)NiB(C(6)H(3)(CF(3))(2))(4), the key intermediate in these reactions is (PNP)Ni(+), [(PNP)Ni](+), in which one Si-C bond (together with N and two P) donates to Ni. This makes this Si-C bond subject to nucleophilic attack by F(-), triflate, and alkoxide/ether (from THF). This σ(Si-C) complex binds CO in the time of mixing and also binds chloride, both at nickel. Evidence is offered of a "self-healing" process, where the broken Si-C bond can be reformed in an equilibrium process. (PNP)Ni(+) reacts rapidly with H(2) to give (PN(H)P)NiH(+), which can be deprotonated to form (PNP)NiH. A variety of nucleophilic attacks (and THF polymerization) on the coordinated Si-C bond are envisioned to occur perpendicular to the Si-C bond, based on the character of the LUMO of (PNP)Ni(+).     

Mechanism of protonation of [Pt(3)(mu-PBu(t)(2))3(H)(CO)2], yielding the hydride-bridged [Pt(3)(mu-PBu(t)(2))2(mu-H)(PBu(t)(2)H)(CO)2]OTf (Tf=CF(3)SO(2)), and the spectroscopic and theoretical characterization of a kinetic intermediate

The reaction of the Pt(I)Pt(I)Pt(II) triangulo cluster Pt(3)(micro-PBu(t)()(2))(3)(H)(CO)(2) (1) with TfOH (Tf = CF(3)SO(2)) affords the hydride-bridged cationic derivative [Pt(3)(mu-PBu(t)()(2))(2)(mu-H)(PBu(t)()(2)H)(CO)(2)]OTf (2). With TfOD the reaction gives selectively [Pt(3)(mu-PBu(t)(2))(2)(mu-D)(PBu(t)(2)H)(CO)(2)]OTf (2-D(1)), implying that the proton is transferred to a metal center while a P-H bond is formed by the reductive coupling of one of the bridging phosphides and the terminal hydride ligand of the reagent. The reaction proceeds through the formation of a thermally unstable kinetic intermediate which was characterized at low temperatures, and was suggested to be the CO-hydrogen-bonded (or protonated) [Pt(3)(mu-PBu(t)(2))(3)(H)(CO)(2)].HOTf (3). An ab initio theoretical study predicts a hydrogen-bonded complex or a proton-transfer tight ion pair as a possible candidate for the structure of the kinetic intermediate.     

Trinuclear nickel complexes with triplesalen ligands: simultaneous occurrence of mixed valence and valence tautomerism in the oxidized species

The coordination chemistries of the triple tetradentate triplesalen ligands H(6)talen, H(6)talen(t)(-)(Bu)(2), and H(6)talen(NO)(2) have been investigated with nickel(II). These triplesalen ligands provide three salen-like coordination environments bridged in a meta-phenylene arrangement by a phloroglucinol backbone. The structures of the complexes [(talen)Ni(II)(3)], [(talen(t)(-)(Bu)(2)Ni(II)(3)], and [(talen(NO)(2)Ni(II)(3)] have been determined by single-crystal X-ray diffraction. All three compounds are composed of neutral trinuclear complexes with square-planar coordinated Ni(II) ions in a salen-like coordination environment. Whereas the overall molecular structure of [(talen(NO)(2)Ni(II)(3)] is nearly planar, the structures of [(talen)Ni(II)(3)] and [(talen(t)(-)(Bu)(2)Ni(II)(3)] are bowl-shaped as a result of ligand folding. The strongest ligand folding occurs at the central nickel-phenolate bond of [(talen(t)(-)(Bu)(2)Ni(II)(3)], resulting in the formation of a chiral hemispherical pocket. The dependence of the physical properties by the substituents on the terminal phenolates has been studied by FTIR, resonance Raman, UV-vis-NIR absorption, and electrochemistry. The three nickel-salen subunits are electronically interacting via the pi system of the bridging phloroglucinol backbone. The strength of this interaction is mediated by two opposing effects: the electron density at the terminal phenolates and the folding of the ligand at the central phenolates. The parent complex [(talen)Ni(II)(3)] is irreversibly oxidized at 0.32 V versus ferrocenium/ferrocene (Fc(+)/Fc), whereas [(talen(t)(-)(Bu)2)Ni(II)(3)] and [(talen(NO)(2)Ni(II)(3)] exhibit reversible oxidations at 0.22 V versus Fc(+)/Fc and 0.52 V versus Fc(+)/Fc, respectively. The oxidized species [(talen(t)(-)(Bu)(2)Ni(3)](+) and [(talen(NO)(2)Ni(3)](+) undergo a valence-tautomeric transformation involving a Ni(III) and a phenoxyl radical species, as observed by EPR spectroscopy. Thus, these oxidized forms exhibit the phenomena of valence tautomerism and mixed valence simultaneously. The extent of delocalization of the radical species and of the Ni(III) species is discussed.     

FTIR detection of protonation/deprotonation of key carboxyl side chains caused by redox change of the Cu(A)-heme a moiety and ligand dissociation from the heme a3-Cu(B) center of bovine heart cytochrome c oxidase

FTIR spectral changes of bovine cytochrome c oxidase (CcO) upon ligand dissociation from heme a(3)() and redox change of the Cu(A)-heme a moiety (Cu(A)Fe(a)()) were investigated. In a photosteady state under CW laser illumination at 590 nm to carbonmonoxy CcO (CcO-CO), the C-O stretching bands due to Fe(a3)()(2+)CO and Cu(B)(1+)CO were identified at 1963 and 2063 cm(-)(1), respectively, for the fully reduced (FR) state [(Cu(A)Fe(a)())(3+)Fe(a3)()(2+)Cu(B)(1+)] and at 1965 and 2061 cm(-)(1) for the mixed valence (MV) state [(Cu(A)Fe(a)())(5+)Fe(a3)()(2+)Cu(B)(1+)] in H(2)O as well as in D(2)O. For the MV state, however, another band due to Cu(B)(1+)CO was found at 2040 cm(-)(1), which was distinct from the alpha/beta conformers in the spectral behaviors, and therefore was assigned to the (Cu(A)Fe(a)())(4+)Fe(a3)()(3+)Cu(B)(1+)CO generated by back electron transfer. The FR-minus-oxidized difference spectrum in the carboxyl stretching region provided two negative bands at 1749 and 1737 cm(-)(1) in H(2)O, which were apparently merged into a single band with a band center at 1741 cm(-)(1) in D(2)O. Comparison of these spectra with those of bacterial enzymes suggests that the 1749 and 1737 cm(-)(1) bands are due to COOH groups of Glu242 and Asp51, respectively. A similar difference spectrum of the carboxyl stretching region was also obtained between (Cu(A)Fe(a)())(3+)Fe(a3)()(2+)Cu(B)(1+)CO and (Cu(A)Fe(a)())(5+)Fe(a3)()(2+)Cu(B)(1+)CO. The results indicate that an oxidation state of the (Cu(A)Fe(a)()) moiety determines the carboxyl stretching spectra. On the other hand, CO-dissociated minus CO-bound difference spectra in the FR state gave rise to a positive and a negative peaks at 1749 and 1741 cm(-)(1), respectively, in H(2)O, but mainly a negative peak at 1735 cm(-)(1) in D(2)O. It was confirmed that the absence of a positive peak is not caused by slow deuteration of protein. The corresponding difference spectrum in the MV state showed a significantly weaker positive peak at 1749 cm(-)(1) and an intense negative peak at 1741 cm(-)(1) (1737 cm(-)(1) in D(2)O). The spectral difference between the FR and MV states is explained satisfactorily by the spectral change induced by the electron back flow upon CO dissociation as described above. Thus, the changes of carboxyl stretching bands induced both by oxidation of (Cu(A)Fe(a)()) and dissociation of CO appear at similar frequencies ( approximately 1749 cm(-)(1)) but are ascribed to different carboxyl side chains.     

Five-coordinate aluminum bromides: synthesis, structure, cation formation, and cleavage of phosphate ester bonds

The alkane elimination reaction between Salen((t)Bu)H(2) ligands and diethylaluminum bromide was used to prepare three Salen aluminum bromide compounds salen((t)Bu)AlBr (1) (salen = N,N'-ethylenebis(3,5-di-tert-butylsalicylideneimine)), salpen((t)Bu)AlBr (2) (salpen = N,N'-propylenebis(3,5-di-tert-butylsalicylideneimine)), and salophen((t)Bu)AlBr (3) (salophen = N,N'-o-phenylenenebis(3,5-di-tert-butylsalicylideneimine)). The compounds contain five-coordinate aluminum either in a distorted square pyramidal or a trigonal bipyramidal environment. The bromide group in these compounds could be displaced by triphenylphosphine oxide or triphenyl phosphate to produce the six-coordinate cationic aluminum compounds [salen((t)Bu)Al(Ph(3)PO)(2)]Br (4), [salpen((t)Bu)Al(Ph(3)PO)(2)]Br (5), [salophen((t)Bu)Al(Ph(3)PO)(2)]Br (6), and [salophen((t)Bu)Al[(PhO)(3)PO)](2)]Br (7). All the compounds were characterized by (1)H, (13)C, (27)Al, and (31)P NMR, IR, mass spectrometry, and melting point. Furthermore, compounds 1-3 and 5-7 were structurally characterized by single-crystal X-ray diffraction. Compounds 1-3 dealkylated a series of organophosphates in stoichiometric reactions by breaking the ester C-O bond. Also, they were catalytic in the dealkylation reaction between trimethyl phosphate and added boron tribromide.     

Intermediates in the Rh-catalysed dehydrocoupling of phosphine-borane

Active species, product distributions and a suggested catalytic cycle are reported for the dehydrocoupling of the phosphine-borane H(3)B·P(t)Bu(2)H to give HP(t)Bu(2)BH(2)P(t)Bu(2)BH(3) using the [Rh(COD)(2)][BAr(F)(4)] pre-catalyst.