Photolytic Reductive Elimination of White Phosphorus from a Mononuclear cyclo-P4 Transition Metal Complex

被引:16
作者
Mandla, Kyle A. [1 ]
Moore, Curtis E. [1 ]
Rheingold, Arnold L. [1 ]
Figueroa, Joshua S. [1 ]
机构
[1] Univ Calif San Diego, Dept Chem & Biochem, 9500 Gilman Dr MC 0358, La Jolla, CA 92093 USA
基金
美国国家科学基金会;
关键词
main-group chemistry; molybdenum; photochemistry; photoelimination; white phosphorus; P-4; ACTIVATION; LIGAND; TETRAPHOSPHACYCLOBUTADIENE; REACTIVITY; AS-4;
D O I
10.1002/anie.201809042
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Elemental white phosphorus (P-4) is well recognized as a critical precursor to organophosphorus compounds. However, regulatory constraints stemming from the toxic and pyrophoric nature of white phosphorus have significantly limited its accessibility. Herein is described a new approach to white phosphorus storage and release based on a unique example of photolytic reductive elimination of the tetrahedral P-4 molecule from a mononuclear cyclo-P-4 molybdenum complex. The latter functions as an air-stable, chemically-deactivated source of white phosphorus. The system features efficient photo-release of white phosphorus using inexpensive violet LED sources. Additionally, high-yield recapture of unspent white phosphorus by the molybdenum center can be achieved by post-photolysis heating at convenient temperatures.
引用
收藏
页码:1779 / 1783
页数:5
相关论文
共 50 条
[1]  
[Anonymous], 1998, J. Phys. Chem. Ref. Data, Monograph
[2]  
[Anonymous], 2000, A Guide to Organophosphorus Chemistry
[3]   Activation of White Phosphorus by Low-Valent Group 5 Complexes: Formation and Reactivity of cyclo-P4 Inverted Sandwich Compounds [J].
Camp, Clement ;
Maron, Laurent ;
Bergman, Robert G. ;
Arnold, John .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (50) :17652-17661
[4]   P4 Activation by Late-Transition Metal Complexes [J].
Caporali, Maria ;
Gonsalvi, Luca ;
Rossin, Andrea ;
Peruzzini, Maurizio .
CHEMICAL REVIEWS, 2010, 110 (07) :4178-4235
[5]   Comparative Measure of the Electronic Influence of Highly Substituted Aryl Isocyanides [J].
Carpenter, Alex E. ;
Mokhtarzadeh, Charles C. ;
Ripatti, Donald S. ;
Havrylyuk, Irena ;
Kamezawa, Ryo ;
Moore, Curtis E. ;
Rheingold, Arnold. L. ;
Figueroa, Joshua S. .
INORGANIC CHEMISTRY, 2015, 54 (06) :2936-2944
[6]  
Cavaill A., 2018, ANGEW CHEM, V130, P1892
[7]   Synthesis and Reactivity of an End-Deck cyclo-P4 Iron Complex [J].
Cavaille, Anthony ;
Saffon-Merceron, Nathalie ;
Nebra, Noel ;
Fustier-Boutignon, Marie ;
Mezailles, Nicolas .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (07) :1874-1878
[8]   Safe P4 reagent in a reusable porous coordination network [J].
Choi, Wanuk ;
Ohtsu, Hiroyoshi ;
Matsushita, Yoshitaka ;
Kawano, Masaki .
DALTON TRANSACTIONS, 2016, 45 (15) :6357-6360
[9]  
Corbridge D.E. C., 2000, PHOSPHORUS 2000, V1st
[10]   Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus [J].
Cossairt, Brandi M. ;
Piro, Nicholas A. ;
Cummins, Christopher C. .
CHEMICAL REVIEWS, 2010, 110 (07) :4164-4177