Single-site N-N bond cleavage by Mo(iv): Possible mechanisms of hydrazido(1-) to nitrido conversion

Difranco S.A.; Staples R.J.; Odom A.L.

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Single-site N-N bond cleavage by Mo(iv): Possible mechanisms of hydrazido(1-) to nitrido conversion

机译：Mo（iv）单点N-N键断裂：肼基（1-）转化为亚硝基的可能机理

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Mo(NMe_2)_4 and the tridentate, dipyrrolyl ligand H_2dpma~(mes) were found to form 5-coordinate Mo(NMe_2)_2(dpma~(mes)) (1), which exhibits spin-crossover behaviour in solution. The complex is a ground state singlet with a barrier of 1150 cm~(-1) for production of the triplet in d8-toluene. The complex reacts with 1,1-disubstituted hydrazines or O-benzylhydroxylamine to produce nitrido MoN(NMe_2)(dpma~(mes)). The mechanism of the 1,1-dimethylhydrazine reaction with 1 was examined along with the mechanism of substitution of NMe_2 with H_2NNMe_2 in a diamagnetic zirconium analogue. The proposed mechanism involves production of a hydrazido(1-) intermediate, Mo(NMe_2)(NHNMe_2)(dpma mes), which undergoes an α,β-proton shift and N-N bond cleavage with metal oxidation to form the nitrido. The rate law for the reaction was found to be -d[1]/dt = kobs[1][hydrazine] by initial rate experiments and examination of the full reaction profile. This conversion from hydrazido(1-) to nitrido is somewhat analogous to the proposed mechanism for O-O bond cleavage in some peroxidases.

机译：发现Mo（NMe_2）_4和三齿二吡咯基配体H_2dpma〜（mes）形成5配位的Mo（NMe_2）_2（dpma〜（mes））（1），在溶液中表现出自旋交叉行为。该配合物是基态单线态，具有1150 cm〜（-1）的势垒，可用于生产d8-甲苯中的三重态。该配合物与1，1-二取代的肼或O-苄基羟胺反应生成亚硝基的MoN（NMe_2）（dpma〜（mes））。研究了1，1-二甲基肼与1的反应机理，以及在反磁性锆类似物中NMe_2被H_2NNMe_2取代的机理。拟议的机制涉及生产肼（1-）中间体Mo（NMe_2）（NHNMe_2）（dpma mes），该中间体会经历α，β质子移位和N-N键断裂，并被金属氧化形成亚硝基。通过初始速率实验和检查整个反应曲线，发现反应的速率定律为-d [1] / dt = kobs [1] [肼]。从肼基（1-）转化为亚硝基的转化过程与某些过氧化物酶中O-O键裂解的拟议机理有些相似。

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《Dalton transactions: An international journal of inorganic chemistry》 |2013年第7期|共10页
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Difranco S.A.; Staples R.J.; Odom A.L.;
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1. Single-site N-N bond cleavage by Mo(iv): Possible mechanisms of hydrazido(1-) to nitrido conversion [J] . Difranco S.A., Staples R.J., Odom A.L. Dalton transactions: An international journal of inorganic chemistry . 2013,第7期

机译：Mo（iv）单点N-N键断裂：肼基（1-）转化为亚硝基的可能机理
2. N-N Bond Cleavage of Mid-Valent Ta(IV) Hydrazido and Hydrazidium Complexes Relevant to the Schrock Cycle for Dinitrogen Fixation [J] . Andrew J. Keane, Peter Y. Zavalij, Lawrence R. Sita Journal of the American Chemical Society . 2013,第26期

机译：与Schrock循环有关的中价Ta（IV）肼基和羟基配合物的N-N键裂解
3. N-N Bond Cleavage of Organohydrazines by Molybdenum(II)and Tungsten(II)Complexes Containing a Linear Tetraphosphine Ligand.Formation of Nitrido or Imido Complexes and Their Reactivities [J] . Daisuke Watanabe, Sumie Gondo, Hidetake Seino Organometallics . 2007,第20期

机译：含线性四膦配体的钼（II）和钨（II）配合物对有机肼的N-N键裂解Nitrido或Imido配合物的形成及其反应性
4. Computational and experimental study of bond cleavage mechanisms in phospho-serine peptide ECD and ETD MS [C] . Christopher Moss, Thomas W. Chung, Frantisek Turecek American Society for Mass Spectrometry Conference on Mass Spectrometry and Allied Topics . 2010

机译：磷酸丝肽ECD和ETD MS中粘合切割机制的计算与实验研究
5. Single-site molybdenum(IV) mediated bond cleavage reactions and ligand parameterization using a chromium(VI) nitrido platform. [D] . DiFranco, Stephen Andrew. 2013

机译：单中心钼（IV）介导的键裂解反应和使用铬（VI）氮离子平台的配体参数化。
6. Borane B-C Bond Cleavage by a Low-Coordinate Iron Hydride Complex and N-N Bond Cleavage by the Hydridoborate Product [O] . Ying Yu, William W. Brennessel, Patrick L. Holland -1

机译：低配位氢化铁络合物的硼烷B-C键裂解和氢硼酸盐产物的N-N键裂解
7. N-N Bond Cleavage of Organohydrazines by Molybdenum(II) and Tungsten(II) Complexes Containing a Linear Tetraphosphine Ligand. Formation of Nitrido or Imido Complexes and Their Reactivities [O] . -1

机译：通过钼（II）和含有线性四膦配体的钨（II）配合物的有机肼的N-N键切割。形成Nitrido或Imido复合物及其反应性
8. User's Guide for Executing OZIPM-4 (Ozone Isopleth Plotting with Optional Mechanisms, Version 4) with CBM-IV (Carbon-Bond Mechanisms-IV) or Optional Mechanisms. Volume 1. Description of the Ozone Isopleth Plotting Package. Version 4 [R] . Hogo, H. , Gery, M. W. 1988

机译：使用CBm-IV（碳键机制-IV）或可选机制执行OZIpm-4（使用可选机制的臭氧等值线图，第4版）的用户指南。第1卷。臭氧等值线图绘制包的描述。版本4

Single-site N-N bond cleavage by Mo(iv): Possible mechanisms of hydrazido(1-) to nitrido conversion

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