U(IV)/LN(III) unexpected mixed site in polymetallic oxalato complexes. Part II. Substitution of U(IV) for Ln(III) in the new oxalates (N2H5)Ln(C2O4)2·nH2O (Ln=Nd, Gd)
lanthanide and oxalateions. The lanthanide atom is coordinated by eight oxygen atoms from four tetradentate oxalateions and one aqua oxygen. Alternating lanthanide and oxalateions form six-membered rings that delimit tunnels running down three directions and occupied by hydrazinium and water molecules. Starting from these lanthanide(III) compounds two isotypic mixed Ln(III)/U(IV) oxalates, (N2H5)0.75[Nd0
U(IV)/Ln(III) unexpected mixed site in polymetallic oxalato complexes. Part I. Substitution of Ln(III) for U(IV) from the new oxalate (NH4)2U2(C2O4)5·0.7H2O
hexagonal tunnels running down the [001] direction. Starting from the uranium (IV) compound A2U2(C2O4)5·0.7H2O with A=NH4+ (1), the mixed U(IV)/Ln(III) oxalates are obtained by partial substitution of U(IV) by Ln(III) in a ten-coordinated site, the charge deficit being compensated by intercalation of supplementary monovalent ions within the tunnels. The distortion of the arrangement in the [001] direction
一种新的草酸铀(IV)铵(NH 4)2 U 2(C 2 O 4)5 ·0.7H 2 O(1)和三种混合铀(IV)-镧系元素(III)草酸酯,(N 2 H 5)2.6 U 1.4 M 0.6(C 2 O 4)5 · x H 2 O(M = Nd(2)和M = Sm(3)),Na 2.56 U 1.44 Nd 0.56(C制备了2 O 4)5 ·7.6H 2 O(4)和Na 3 UCe(C 2 O 4)5 ·10.4H 2 O(5)。化合物的晶体结构1,4和5已经通过单晶X射线衍射来确定。通过直接方法和傅立叶差分技术来解析晶体结构,并针对所有唯一反射,在F 2的基础上通过最小二乘法对晶体结构进行细化。化合物2和3与1同型。晶体学数据:1,六角形,空间群P 6 3 / mmc的,一个= 19.177(3),C ^ = 12.728(4),Ž = 6,- [R 1 = 0.0575 52个参数与1360个反射与我⩾2
Catalytic Silylation of N<sub>2</sub>and Synthesis of NH<sub>3</sub>and N<sub>2</sub>H<sub>4</sub>by Net Hydrogen Atom Transfer Reactions Using a Chromium P<sub>4</sub>Macrocycle
作者:Alexander J. Kendall、Samantha I. Johnson、R. Morris Bullock、Michael T. Mock
DOI:10.1021/jacs.7b11132
日期:2018.2.21
reduction of N2 to N(SiMe3)3 by Na and Me3SiCl, affording up to 34 equiv N(SiMe3)3; (2) stoichiometric reduction of N2 by protons and electrons (for example, the reaction of cobaltocene and collidinium triflate at room temperature afforded 1.9 equiv of NH3, or at -78 °C afforded a mixture of NH3 and N2H4); and (3) the first example of NH3 formation from the reaction of a terminally bound N2 ligand with
Kinetics and Mechanisms of the Oxidation of Hydrazinium Ion (N<sub>2</sub>H<sub>5</sub><sup>+</sup>) by Aqueous Br<sub>2</sub>, Cl<sub>2</sub>, and BrCl. Electrophilicity Scale for Halogens and Interhalogens
作者:Zhongjiang Jia、Murad G. Salaita、Dale W. Margerum
DOI:10.1021/ic991220k
日期:2000.5.1
C, mu = 1.0 M are 1.49 x 10(7), 1.01 x 10(8), and 5.6 x 10(8) for the reactions with Br2, Cl2, and BrCl, respectively. The reactions are postulated to proceed by nucleophilic reaction of N2H5+ with XY electrophiles (XY = Br2, Cl2, BrCl) to form XN2H4+ with Y- and H+ release in the rate-determining step. In the subsequent reactions, we propose that XN2H4+ eliminates X- and H+ rapidly to form N2H3+ and
在过量N2H5 +的酸性溶液中,通过停流和脉冲加速流方法测量了Br2,Cl2和BrCl对N2H5 +的快速氧化。对于与Br2的反应,在25.0摄氏度,mu = 1.0 M时的二级速率常数(M-1 s-1)为1.49 x 10(7),1.01 x 10(8)和5.6 x 10(8), Cl2和BrCl分别。假定该反应通过速率确定步骤中N2H5 +与XY亲电试剂(XY = Br2,Cl2,BrCl)的亲核反应进行,以形成具有Y-和H +释放的XN2H4 +。在随后的反应中,我们建议XN2H4 +快速消除X-和H +以形成N2H3 +和二嗪N2H2,该二嗪被第二个Br2,Cl2或BrCl氧化以快速形成N2。测量化学计量,对于Cl2和BrCl反应确认为1:2。
Ammonia and Hydrazine from Coordinated Dinitrogen by Complexes of Iron(0)
作者:Leslie D. Field、Hsiu L. Li、Scott J. Dalgarno、Ruaraidh D. McIntosh
DOI:10.1002/ejic.201900058
日期:2019.4.16
The iron(0) dinitrogen complexes [Fe(N2)(PP3)] (PP3 = P(CH2CH2PR2)3, R = Ph, iPr, Cy) were synthesized by reduction of the precursor chloro complexes with potassium graphite. On reaction with triflic acid, [Fe(N2)(PP3)] complexes afforded ammonia and hydrazine in yields of up to 23 and 16% respectively. The complex [Fe(N2)(PP3)] which has only been previously synthesized in situ, has now been isolated