Fast atom bombardment,electron impact and chemical ionization mass spectrometry of the neutral 18-electron species M(CO)2(CNR)2(PR′3)2 (MMo or W)

The molybdenum(0) and tungsten(O) complexes of the type M(CO)₂(CNR)₂(PR′₃)₂ have been studied using a variety of mass spectral techniques, viz. fast atom bombardment (FAB), electron impact (EI), and both positive- and negative-ion chemical ionization (PICI and NICI) mass spectrometry. The FABMS technique gave the most structurally informative spectra with the observation of the molecular ions M⁺ (100% relative abundance in the case of MW) and in some instances the pseudomolecular ion (M + H)⁺. Fragmentation ions arising from competitive ligand loss (CO versus RNC versus PR′₃) were observed, as well as those formed by loss of H from fragment ions and dealkylation of RNC ligands. The EI and PICI spectra were not especially useful due to the relatively low thermal stability of these complexes, while the NICI spectra gave an abundance of ions that resulted from ligand redistribution reactions. Of special note were anions that contained M(CO)₄ and M(CO)₃ fragments. Dealkylation of the RNC ligands to give cyanometallate anions was also prevalent.     

Solution behaviour and relative stability of the complexes [MCl2(RNCHCHNR)] and [MCl2(py-2-CHNR)] (M=Pd,Pt;R=C6H4OMe-p)

Even though the α-diimino complexes [MCl₂(RNCHCHNR)] and [MCl₂(py-2-CHNR)] (M=Pd, Pt;R=C₆H₄OMe-p) are poorly soluble in chlorinated solvents, such as chloroform and 1,2-dichloroethane, or in acetonitrile, the electronic and ¹H NMR spectra indicate that these compounds are generally present as undissociate monomers with σ, σ′-N,N′ chelate N-ligands in dilute solutions. Only for [PdCl₂(RNCHCHNR)], some dissociation of the α-diimine occurs in acetonitrile. In dimethylsulfoxide, where the solubility is much higher, no dissociation is observed for the pyridine-2-carbaldimine complexes [MCl₂(py-2-CHNR)], whereas the 1,2-bis(imino) ethane derivatives [MCl₂(RNCHCHNR)] are extensively dissociated through a step-wise process involving intermediates with a σ-N monodentate α-diimino group. As is shown by the course of substitution reactions with 2,2′-bipyridine, the higher stability of [MCl₂(py-2-CHNR)] in dimethylsulfoxide is mainly due to thermodynamic factors (ground state stabilization for the presence of stronger MN bonds) rather than by kinetic factors (higher activation energy for steric strain in the activation states or transients).     

MonodentateN coordination of 1aza4oxo1,3butadienes [R1NC(R2)C(R3)O] to platinum(II). X-ray structure of trans-[PtCl2(PEt3){σ-N-(t-BuNCHC(Me)O)}]

Reaction of dimeric trans-[PtCl₂(PR₃)]₂ with 1-aza-4-oxo-1,3-butadienes [R¹NC(R²)C(R³)O, R³ = Me, Ph, OMe, NEt₂] in a 1:2 molar ratio results in almost quantitative formation of mononuclear complexes trans·[PtCl₂(PR₃){σ-N-(R¹NC(R²)C(R³)O)}]. The ligands are bonded in the monodentate σ-N bonding mode to the platinum(II) centre. This has been established by an X-ray structure determination of trans-[PtCl₂(PEt₃){σ-N-(t-BuNCHC(Me)O)}]. Crystals of the latter compound are orthorhombic with space group Pc2₁n; cell constants are a = 14.712(3), b = 15.053(2), c = 9.025(5) Å, Z= 4 and R_w = 0.056 for 3281 reflections. The 1aza4oxol,3butadiene (α-iminoketone for R³ is alkyl or aryl) has the E-configuration about the imine bond (CN 1.34(4) Å), with a C(5)C(6) distance of 1.44(5) Å and a NC(5)/ C(6)O torsion angle of 89(4)°. As a result of this ligand conformation, the acetyl hydrogen atoms are positioned (on average) into the neighbourhood of the Pt-atom above the Pt-coordination plane. Infrared and NMR (¹H, ¹³C, ³¹p) data show that these structural features are also predominant in solution.     

Synthesis of heterodinuclear FeRu(CO)6(R-DAB(6e))(R-DABRNC(H)C(H)NR) Part XV. Comparison of the reactivities of heterodinuclear FeRu(CO)6(R-DAB(6e)) and homodinuclear analogues M2(CO)6(R-DAB(6e)) (M = Fe,Ru). Single-crystal x-ray structures of FeRu(CO)6(i-Pr-DAB(6e)) and FeRu(CO)5(i-Pr-DAB(4e))(C3H4)

The reactions of Fe(CO)₃(R-DAB; R¹, H(4e)) (1a: R = i-Pr, R¹ = H; 1b: R = t-Bu, R¹ = H; 1c: R = c-Hex, R¹ = H; 1e: R = p-Tol, R¹ = H; 1f: R = i-Pr, R¹ = Me) with Ru₃(CO)₁₂ and of Ru(CO)₃(R-DAB; R¹, H(4e)) (2a: R = i-Pr, R¹ = H; 2d: R = CH(i-Pr)₂, R¹ = H) with Fe₂(CO)₉ in refluxing heptane both afforded FeRu(CO)₆(R-DAB; R¹, H(6e)) (3) in yields between 50 and 65%.The coordination mode of the ligand has been studied by a single crystal X-ray structure determination of FeRu(CO)₆(i-Pr-DAB(6e)) (3a). Crystals of 3a are monoclinic, space group P2₁/a, with four molecules in a unit cell of dimensions: a = 22.436(3), b = 8.136(3), c = 10.266(1) Å and β = 99.57(1)°. The structure was refined to R = 0.049 and R_w = 0.052 using 3045 reflections above the 2.5σ(I) level. The molecule contains an FeRu bond of 2.6602(9) Å, three terminally bonded carbonyls to Fe, three terminally bonded carbonyls to Ru and bridging 6e donating i-Pr-DAB ligand. The i-Pr-DAB ligand is coordinated to Ru via N(1) and N(2) occupying an apical and equatorial site respectively (RuN(1) = 2.138(4) RuN(2) = 2.102(3) Å). The C(2)N(2) moiety of the ligand is η²-coordinated to Fe with C(2) in an apical and N(2) in an equatorial site (FeC(2) = 2.070(5) and FeN(2) = 1.942(3) Å).The ¹H and ¹³C NMR data indicate that in all FeRu(CO)₆(R-DAB(6e)) complexes (3a to 3f) exclusively η²-CN coordination to the Fe atom and not to the Ru atom is present irrespective of whether 3 was prepared by reaction of Fe(CO)₃(R-DAB(4e)) (1) with Ru₃(CO)₁₂ or by reaction of Ru(CO)₃(R-DAB(4e)) (2) with Fe₂(CO)₉. In the case of FeRu(CO)₆(i-Pr-DAB; Me, H(6e)) (3f) the NMR data show that only the complex with the C(Me)N moiety of the ligand σ-N coordinated to the Ru atom and the C(H)N moiety η²-coordinated to the Fe atom was formed. Variable temperature NMR experiments up to 140 °C showed that the α-diimine ligand in 3a is stereochemically rigid bonded.FeRu(CO)₆(R-DAB(6e)) (3a and 3e) reacted with allene to give FeRu(CO)₅(R-DAB(4e))(C₃H₄) (4a and 4e). A single crystal X-ray structure determination of FeRu(CO)₅(i-Pr-DAB(4e))(C₃H₄) (4a) was performed. Crystals of 4a are triclinic, space group P1, with two molecules in a unit cell of dimensions: a = 9.7882(7), b = 12.2609(9), c = 8.3343(7) Å, α = 99.77(1)°, β = 91.47(1)° and γ = 86.00(1)°. The structure was refined to R = 0.028 and R_w = 0.043 using 4598 reflections above the 2σ(I) level. The molecule contains an FeRu bond of 2.7405(7) Å and three terminally bonded carbonyls to iron. Two carbonyls are terminally bonded to the Ru atom together with a chelating 4e donating i-Pr-DAB ligand [RuN = 2.110(1) (mean)]. The allene ligand is coordinated in an η³-allylic fashion to the Fe atom while the central carbon of the allene moiety is σ-bonded to the Ru atom (FeC(14) = 2.166(3), FeC(15) = 1.970(2), FeC(16) = 2.127(3) and RuC(15) = 2.075(2) Å). The ¹H and ¹³C NMR data show that in solution the coordination modes of the R-DAB and the allene ligands are the same as in the solid state.Thermolysis reactions of 3a with R-DAB or carbodiimides gave decomposition and did not afford C(imine)C(reactant) coupling products. Thermolysis reactions of 3a with M₃(CO)₁₂ (M = Ru, Os) and Me₃NO gave decomposition. When the reaction of 3a with Me₃NO was performed in the presence of dimethylacetylenedicarboxylate (DMADC) the known complex FeRu(CO)₄(i-Pr-DAB(8e))(DMADC) (5a) was formed in low yield. In 5a the R-DAB ligand is in the 8e coordination mode with both the imine bonds η²-coordinated to iron. The acetylene ligand is coordinated in a bridging fashion, parallel with the FeRu bond.     

Transition metal complexes with sulfur ligands. XIX. Mono- and bis-alkylation of [Ru(II)L1L2dttd] complexes controlled by the ligands L as well as the charge of the resulting compounds (dttd2−=2,3:8,9-dibenzo-1,4,7,10-tetrathiadecane(−2), L1L2PPh3; L1L2PMe3; L1PPh3, L2PMe3)

The alkylation of the thiolato-S atoms of the dttd- ligand in [RuL₁L₂dttd] complexes was investigated (L₁L₂PPh₃; L₁L₂PMe₃; L₁PPh₃, L₂PMe₃; dttd²⁻=2,3:8,9-dibenzo-1,4,7,10-tetrathiadecane(−2)). The substitution lability of the phosphine ligands L₁ and L₂ determines whether one or both of the thiolato-S atoms are alkylated when [RuL₁L₂dttd] is reacted with alkylhalides. [Ru(PPh₃)₂dttd], in which one PPh₃ is substitution labile, is doubly alkylated on reaction with CH₃I yielding [Ru(PPh₃)I(Me₂-dttd)]I (Me₂-dttd=1,10-dimethyl-2,3:8,9-dibenzo-1,4,7,10-tetrathiadecane). Reaction of the substitution inert phosphine complexes [Ru(PMe₃)₂dttd] and [Ru(PPh₃)(PMe₃)dttd] with CH₃I yields the monoalkylated derivatives [Ru(PMe₃)₂(Me-dttd)]I and [Ru(PPh₃)(PMe₃)(Me- dttd)]I, respectively. Analogously, ethyl as well as bromine derivatives can be obtained. The cation in [Ru(PPh₃)X(Me₂-dttd)]X (XI, Br) proves to be substitution inert under ordinary conditions; the anion X can be exchanged for other singly charged anions via [Ru(PPh₃)X(Me₂dttd)]₂SO₄. In concentrated H₂SO₄, [Ru(PPh₃)Br(Me₂-dttd)]Br could be reacted to give [Ru(Br₂)(Me₂dttd)]. All compounds were characterized spectroscopically as well as by elemental analyses. The structure of [Ru(PPh₃)I(Me₂- dttd)]I was determined by X-ray structure analysis.[Ru(PPh₃)I(Me₂-dttd)]I (1) crystallizes from CH₂Cl₂ as 1·3CH₂Cl₂ in the monoclinic space group P2₁/c with the following unit cell dimensions: a= 20.103(0.03), b=11.148(0.009), c=26.985(0.03) Å; β=130.71(0.07)°, V=4584(3) ų and Z=4. The structure refinement stopped at R₁=8.86 and R₂= 10.44% because of disorder of the CH₂Cl₂ solvate molecules. In the cation of 1 Ru is coordinated pseudo-octahedrally by I-, P- and four thioether-S atoms.     

125Te Mössbauer spectra of the intercalation compound (Te2)2(I2)

The quadrupole split asymmetric ¹²⁵Te Mössbauer spectrum recorded from the compound (Te₂)₂(I₂), in which monomolecular planar layers of iodine molecules are intercalated between layers of tellurium, is a reflection of the distorted environment of tellurium atoms in a two-dimensional layered compound in which the elongated flat crystals are preferentially orientated. The differences between the Mössbauer parameters recorded from (Te₂)₂(I₂) and those recorded from elemental tellurium and the tellurium(0) species in the compound Te₃Cl₂ are associated with small differences between the environments of tellurium in the three compounds. The Mössbauer spectra recorded from (Te₂)₂(I₂) are consistent with a recently proposed model on which the electronic band structure of (Te₂)₂(I₂) has been derived.     

Binuclear rhodium carbonyl halide complexes containing the 1,1-bis(diphenylphosphino)ethene ligand,and the crystal structure of [Rh2Cl2(μ-CO){Ph2PC(CH2)PPh2}2]

Treatment of [RhCl(CO)₂]₂ with 1,1-bis(diphenylphosphino)ethene (dppee) yields the cationic binuclear rhodium complex [Rh₂(μ-Cl)(CO)₂(μ-CO)(dppee)₂]⁺ which may be isolated as the [RhCl₂(CO)₂]⁻ salt at low temperature (230 K) but which readily forms the Cl⁻ salt on allowing the solution to warm to room temperature. On bubbling nitrogen through a solution of this cationic complex at room temperature, the monocarbonyl species, [Rh₂Cl₂(μ-CO)(dppee)₂] is obtained. The crystal structure of this complex has been determined. The crystals are orthorhombic, space group Pnca, a = 29.98(3), b = 23.70(2), c = 14.78(3) Å, Z = 8. Using 3019 unique reflections the structure was refined to R = 0.091. The rhodium-rhodium distance is 2.650(14) Å. Direct rhodium NMR data are reported for these complexes.     

He(I) and He(II) photoelectron spectra of Hyprrole-2-CHN′t-Bu and the biscarbonyl Rh(I) and Ir(I) complexes of its anion

The He(I) and He(II) photoelectron spectra of a series of [(LL)M(CO)₂] (LL = pyrrole-2-CHN′ R; R = t-Bu; M = Rh, Ir) complexes are reported. Assignments are proposed based on He(I)/He(II) intensity differences, on molecular orbital calculations of related complexes and of free ligands, and by comparison with the spectra of the free ligands Hpyrrole-2-CHN′t-Bu, Hpyrrole-2-carbaldehyde and Hpyrrole.The electronic structure of the complexes is discussed and conclusions are drawn about the metal-ligand interaction.     

酵母双杂交筛选与果蝇C(2)M相互作用的蛋白

同源染色体联会时形成的联会复合体(Synaptonemal complex, SC)是由减数分裂前期Ⅰ多种蛋白质聚集而成的超级复合结构。生殖细胞特异性的核蛋白C(2)M(Crossover suppressor on 2 of Manheim)在染色体上高度聚集可以诱导SC的形成。本文采用酵母双杂交方法,利用C(2)M的诱饵表达载体筛选果蝇cDNA文库,共发现40个可能与C(2)M相互作用的蛋白,包括多种DNA及组蛋白结合蛋白、ATPase、转录调节因子。从筛选的结果中,选取wech和Psf1基因构建了转基因果蝇,并在生殖细胞中进行了基因沉默,结果显示联会复合体的消失受到延迟。上述结果表明Wech和Psf1蛋白可能与C(2)M形成复合物,共同参与联会复合体的形成或其稳定性的维持。     

曲霉M—2降解有机磷农药(甲胺磷)的研究

分离了一株能降解甲胺磷的曲霉Ｍ－２。Ｍ－２能以甲胺磷为唯一碳源、氮源及磷源生长。在０．２％甲胺磷无机盐发酵液中,培养５ｄ后,降解率达８１．５％。添加少量有机氮能促进Ｍ－２对甲胺磷的利用。     

Bis(heptalene) “submarine” metal dimer sandwich compounds (C12H10)2M2 (M = Ti, V, Cr, Mn, Fe, Co, Ni)

The bis(heptalene)dimetal complexes (C₁₂H₁₀)₂M₂ of the first row transition metals from Ti to Ni are predicted by density functional theory to exhibit “submarine” sandwich structures with a pair of metal atoms sandwiched between the two heptalene rings. For the early transition metal derivatives (C₁₂H₁₀)₂M₂ (M = V, Cr) there are two types of such structures. In one structural type the metals are sandwiched between two heptahapto heptalene rings with metal-metal distances (3.5–3.8 Å) too long for direct metal-metal bonding. The other type of (C₁₂H₁₀)₂M₂ (M = V, Cr, Mn) structure has a pair of bonded metal atoms sandwiched between a fully bonded heptalene ligand and a heptalene ligand bonded to the metals only through an eight-carbon heptafulvene subunit, leaving an uncomplexed cis-1,3-diene unit. The formal metal-metal bond orders in these latter structures are 3, 2, and 1 for M = V, Cr, and Mn with predicted bond lengths of 2.5, 2.7, and 2.8 Å, respectively. For (C₁₂H₁₀)₂Fe₂ a singlet structure with each iron atom sandwiched between a hexahapto and a tetrahapto heptalene ring is energetically preferred over an alternate structure with ferrocene-like iron atoms sandwiched between two pentahapto heptalene rings. Partial bonding of each heptalene ring to the metal atoms occurs in the late transition metal derivatives (C₁₂H₁₀)₂M₂ (M = Co, Ni). This leads to an unsymmetrical structure for the cobalt derivative and a structure for the nickel derivative with each nickel atom sandwiched between a trihapto ligand and a tetrahapto ligand.

Cyclopentadienyl iron xanthate complexes. Crystal and molecular structure and electrochemical reduction of η-C5R5Fe(CO)2(η1-SC(S)OEt) (RH or CH3)

Complexes η-C₅R₅Fe(CO)₂(η¹-SC(S)OEt) (RH, (1) and RCH₃ (2)) have been analysed by X-ray diffraction techniques. 1: P2₁2₁2₁ 11.3560(5), 10.8595(4), 10.1158(3) Å, Z=4; 1023 observed reflexions, R and R_w 0.069 and 0.073. 2: Pbca, 15.6907(11), 15.4566(13), 14.3083(11) Å, Z=8; 2271 observed reflexions, R and R_w being 0.071, 0.073. The coordination is quite similar for both compounds with the xanthate monodentate ligand almost perpendicular to the ring planes and a relative twist, one from each other of about 10°. The reductive electrochemistry of both complexes has been examined by cyclic voltammetry and coulometry. In a carbon electrode the first-one electron reduction step can be ascribed to the formation of corresponding carbonyl dimers. In a mercury electrode, the first reduction step of 1 leads to a bond rupture process with formation of a mercury compound [CpFe(CO)₂]₂Hg and further reduction to the anion CpFe(CO)₂⁻. However, the behaviour of the pentamethylcyclopentadienyl complex (2) is quite different, and it is reduced in a three step process.     

Theoretical studies on all-metal binuclear sandwich-like complexes M2(η4-E4)2 (M=Al, Ga, In; E=Sb, Bi)

A series of all-metal binuclear sandwich-like complexes with the formula M(2)(η(4)-E(4))(2) (M=Al, Ga, In; E=Sb, Bi) was studied by density functional theory (DFT). The most stable conformer for each of the M(2)(η(4)-E(4))(2) species is the staggered one with D (4d) symmetry. The centred metal-metal bond in each M(2)(η(4)-E(4))(2) species is a covalent single bond, with the main contributors to these covalent bonds being the a(1) and e orbitals. For all these species, the interactions between the centred metal atoms and the all-metal ligands are covalent; η(4)-Sb (4) (2-) has a stronger ability to stabilize metal-metal bonds than η(4)-Bi (4) (2-). Nucleus-independent chemical shifts (NICS) values and molecular orbital (MO) analysis reveal that the all-metal η(4)-Sb (4) (2-) and η(4)-Bi (4) (2-) ligands in M(2)(η(4)-E(4))(2) possess conflicting aromaticity (σ antiaromaticity and π aromaticity), which differs from the all-metal multiple aromatic unit Al (4) (2-). In addition, all of these M(2)(η(4)-E(4))(2) species are stable according to the dissociation energies of M(2)(η(4)-E(4))(2)?→?2 M(η(4)-E(4)) and M(2)(η(4)-E(4))(2)?→?2 M?+?2E(4), and these stable species can be synthesized by two-step substitution reactions: CpZnZnCp?+?2E (4) (2-) →?[E(4)ZnZnE(4)](2-)?+?2Cp(-) and [E(4)ZnZnE(4)](2-)?+?2 M (2) (+) →?E(4)MME(4)?+?2Zn(+).