A stable silicon(0) compound with a Si=Si double bond

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl4 {where L: is:C[N(2,6-Pri2-C6H3)CH]2 and Pri is isopropyl} produces L:(Cl)Si-Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 +/- 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si-Si(Cl):L and L:Si=Si:L.     

Tetramesityldisilene, a stable compound containing a silicon-silicon double bond

Irradiation of 2,2-bis(2,4,6-trimethylphenyl)hexamethyltrisilane in hydrocarbon solution produces tetramesityldisilene, which can be isolated as a yellow-orange solid stable to room temperature and above in the absence of air. Like the olefins of carbon chemistry, tetramesityldisilene undergoes addition reactions across the silicon-silicon double bond.     

A stable compound containing a silicon-silicon triple bond

The reaction of 2,2,3,3-tetrabromo-1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasilane with four equivalents of potassium graphite (KC8) in tetrahydrofuran produces 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyl-2-tetrasilyne, a stable compound with a silicon-silicon triple bond, which can be isolated as emerald green crystals stable up to 100 degrees C in the absence of air. The SiSi triple-bond length (and its estimated standard deviation) is 2.0622(9) angstroms, which shows half the magnitude of the bond shortening of alkynes compared with that of alkenes. Unlike alkynes, the substituents at the SiSi group are not arranged in a linear fashion, but are trans-bent with a bond angle of 137.44(4) degrees.     

Synthesis of a stable compound with fivefold bonding between two chromium(I) centers

Although in principle transition metals can form bonds with six shared electron pairs, only quadruply bonded compounds can be isolated as stable species at room temperature. Here we show that the reduction of {Cr(mu-Cl)Ar'}2 [where Ar' indicates C6H3-2,6(C6H3-2,6-Pri2)2 and Pr indicates isopropyl] with a slight excess of potassium graphite has produced a stable compound with fivefold chromium-chromium (Cr-Cr) bonding. The very air- and moisture-sensitive dark red crystals of Ar'CrCrAr' were isolated with greater than 40% yield. X-ray diffraction revealed a Cr-Cr bond length of 1.8351(4) angstroms (where the number in parentheses indicates the standard deviation) and a planar transbent core geometry. These data, the structure's temperature-independent paramagnetism, and computational studies support the sharing of five electron pairs in five bonding molecular orbitals between two 3d5 chromium(I) ions.     

Ambient-temperature isolation of a compound with a boron-boron triple bond

Homoatomic triple bonds between main-group elements have been restricted to alkynes, dinitrogen, and a handful of reactive compounds featuring trans-bent heavier elements of groups 13 and 14. Previous attempts to prepare a compound with a boron-boron triple bond that is stable at ambient temperature have been unsuccessful, despite numerous computational studies predicting their viability. We found that reduction of a bis(N-heterocyclic carbene)-stabilized tetrabromodiborane with either two or four equivalents of sodium naphthalenide, a one-electron reducing agent, yields isolable diborene and diboryne compounds. Crystallographic and spectroscopic characterization confirm that the latter is a halide-free linear system containing a boron-boron triple bond.     

Cytochrome P450 compound I: capture, characterization, and C-H bond activation kinetics

Cytochrome P450 enzymes are responsible for the phase I metabolism of approximately 75% of known pharmaceuticals. P450s perform this and other important biological functions through the controlled activation of C-H bonds. Here, we report the spectroscopic and kinetic characterization of the long-sought principal intermediate involved in this process, P450 compound I (P450-I), which we prepared in approximately 75% yield by reacting ferric CYP119 with m-chloroperbenzoic acid. The M?ssbauer spectrum of CYP119-I is similar to that of chloroperoxidase compound I, although its electron paramagnetic resonance spectrum reflects an increase in |J|/D, the ratio of the exchange coupling to the zero-field splitting. CYP119-I hydroxylates the unactivated C-H bonds of lauric acid [D(C-H) ~ 100 kilocalories per mole], with an apparent second-order rate constant of k(app) = 1.1 × 10(7) per molar per second at 4°C. Direct measurements put a lower limit of k ≥ 210 per second on the rate constant for bound substrate oxidation, whereas analyses involving kinetic isotope effects predict a value in excess of 1400 per second.     

土壤腐殖酸与~(109)Cd、~(65)Zn及其复合存在的络合物稳定性研究

 应用同位素示踪法和离子交换平衡法测定了 Ｃｄ、Ｚｎ为单一离子及复合存在时．土壤胡敏酸（ＨＡ）和富里酸（ＦＡ）与Ｃｄ、Ｚｎ的络合稳定常数及配位数。结果表明、Ｃｄ、Ｚｎ为单一离子时．ＨＡ－１０９Ｃｄ（６５Ｚｎ）络合物的稳定常数与配位数均大于ＦＡ－１０９Ｃｄ（６５Ｚｎ）络合物稳定常数与配位数，而ＨＡ（ＦＡ）－６５Ｚｎ的稳定常数与配位数大于ＨＡ（ＦＡ）－１０９Ｃｄ。１０９Ｃｄ、６５Ｚｎ为复合体系共存与单一存在相比较．ＨＡ（ＦＡ）－６５Ｚｎ络合物稳定常数与配位数有明显的提高，ＨＡ（ＦＡ）－１０９Ｃｄ络合稳定常数与配位数则明显降低。研究结果说明，在重金属污染土壤上施用大分子的腐殖酸较小分子的腐殖酸更能有效地降低重金属元素的植物有效性，Ｚｎ污染土壤上施用腐殖酸较Ｃｄ污染土壤上施用腐殖酸更能有效地降低重金属元素对植物的毒害。而 Ｃｄ、Ｚｎ复合存在时与单一离子存在时相比较，施用腐殖酸将增加 Ｃｄ污染的危害，而减少Ｚｎ污染的危害。     

A stable bicyclic compound with two Si=Si double bonds

In contrast to carbon, silicon does not readily form double bonds, and compounds containing silicon-silicon double bonds can usually be stabilized only by protection with bulky substituents. We have isolated a silicon analog of spiropentadiene 1, a carbon double-ring compound that has not been isolated to date. In the crystal structure of tetrakis[tri(t-butyldimethylsilyl)silyl]spiropentasiladiene 2, a substantial deviation from the perpendicular arrangement of the two rings is observed, and the silicon-silicon double bonds are shown to be distorted. Spectroscopic data indicate pronounced interaction between two remote silicon-silicon double bonds in the molecule. Silicon-silicon bonds may be more accessible to synthesis than previously assumed.     

高稳系数法在芝麻品种(系)高产稳产性分析中的应用

利用高稳系数法 (HSC)对 2 0 0 1、2 0 0 2年湖北省芝麻区域试验中的品种 (系 )进行高产稳产性分析 ,结果表明不同品种 (系 )的高产稳产性不同 ,“97- 4 13”在 2 0 0 1和 2 0 0 2年均表现出高产稳产性突出的特点 ,“98- 4 15 5”表现高产稳产性较好 ,“AE0 80 9936”高产性优于对照鄂芝 2号 ,“0 0 - 5 10 13”在 2 0 0 2年参加一年区试中表现稳产性好、高产性较好的特点。HSC法与方差分析法相比计算较为简单 ,能更客观反映芝麻品种的高产稳产性     

锌(Ⅱ)-邻菲啰啉络合物线扫极谱法测定血清白蛋白的研究

利用线扫极谱法研究了锌(Ⅱ)-邻菲啰啉(Phen)二元络合物与人血清白蛋白(HSA)的相互作用并建立了以Zn(Ⅱ)-Phen二元配合物为电化学探针测定HSA的分析测试方法。在最佳条件下,还原峰电流的降低值与人血清白蛋白的浓度2.0~20.0mg/L范围内呈线性关系,线性回归方程为ΔIp″(nA)=140.3C(mg/L)+1981.06(ni=16,γ=0.996),检测限为1.301mg/L(3σ)。应用该法测定了模拟样品和健康人血清样品中蛋白质的含量,结果令人满意。     

Stable magnesium(I) compounds with Mg-Mg bonds

The chemistry of the group 2 metals (beryllium, magnesium, calcium, strontium, and barium) is dominated by the +2 oxidation state. Here, we report the reductions of two magnesium(II) iodide complexes with potassium metal in toluene, leading to thermally stable magnesium(I) compounds, (L)MgMg(L) (where L is [(Ar)NC(NPri2)N(Ar)]- or {[(Ar)NC(Me)]2CH}-, Ar is 2,6-diisopropylphenyl, Me is methyl, and Pri is isopropyl) in moderate yields. The results of x-ray crystallographic and theoretical studies are consistent with central Mg2+(2) units that have single, covalent magnesium-magnesium bonding interactions with 2.8508 +/- 0.0012 (standard deviation) and 2.8457 +/- 0.0008 angstrom bond lengths, respectively, and predominantly ionic interactions with the anionic ligands (L).     

Biological populations with nonoverlapping generations: stable points, stable cycles, and chaos

Some of the simplest nonlinear difference equations describing the growth of biological populations with nonoverlapping generations can exhibit a remarkable spectrum of dynamical behavior, from stable equilibrium points, to stable cyclic oscillations between 2 population points, to stable cycles with 4, 8, 16, . . . points, through to a chaotic regime in which (depending on the initial population value) cycles of any period, or even totally aperiodic but boundedpopulation fluctuations, can occur. This rich dynamical structure is overlooked in conventional linearized analyses; its existence in such fully deterministic nonlinear difference equations is a fact of considerable mathematical and ecological interest.     

(Amino)(aryl)carbenes: stable singlet carbenes featuring a spectator substituent

Several (amino)(aryl)carbenes have been shown to be stable at room temperature in solution and in the solid state. Electroneutrality of the carbene center is ensured by the amino group, which has both pi-donor and final sigma-acceptor electronic character. The aryl group remains a spectator substituent, as shown by single-crystal x-ray analysis and by its chemical behavior. Because only one electron-active substituent is needed, numerous stable carbenes will become accessible, which will open the way for new synthetic developments and applications in various fields.