(η5-C5Me5)2U(=P-2,4,6-tBu3C6H2)(OPMe3) Revisited-Its Intrinsic Reactivity toward Small Organic Molecules

被引:18
作者
Wang, Deqiang [1 ]
Hou, Guohua [1 ]
Zi, Guofu [1 ]
Walter, Marc D. [2 ]
机构
[1] Beijing Normal Univ, Dept Chem, Beijing 100875, Peoples R China
[2] Tech Univ Carolo Wilhelmina Braunschweig, Inst Anorgan & Analyt Chem, D-38106 Braunschweig, Germany
基金
中国国家自然科学基金;
关键词
ELECTROPHILIC PHOSPHINIDENE COMPLEXES; BOND-FORMING REACTIONS; TERMINAL PHOSPHINIDENE; IMIDO METALLOCENE; CRYSTAL-STRUCTURE; CHEMISTRY; ACTIVATION; PHOSPHORUS; RUTHENIUM; LIGAND;
D O I
10.1021/acs.organomet.0c00640
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The Lewis base stabilized uranium phosphinidene (eta(5)-C5Me5)(2)U(=P-2,4,6-(Bu3C6H2)-Bu-t)(OPMe3) (2), which was derived from (eta(5)-C5Me5)(2)U(Cl)Me (1) and 2,4,6-(Me3C)(3)C6H2 PHK in toluene in the presence of Me 3 PO, was originally reported in 1996, but since then its reactivity toward small organic molecules has not been extensively explored. This contribution closes this gap, and divergent reactivity patterns are established in the reaction of complex 2 toward (small) organic substrates. For example, complex 2 may release the phosphinidene moiety (2,4,6-(Bu3C6H2P)-Bu-t:) and therefore may act as a source of a (eta(5)-C5Me5)(2)U-II fragment in the presence of Ph2S2, Ph2Se2, bipy, ketazine (Ph2C=N)(2), and conjugated alkynes RC CC CR, forming the disulfido compound (eta(5)-C5Me5)(2) U(SPh)(2) (5), diselenido compound (eta(5)-C5Me5)(2) U(SePh)(2) (6), bipy compound (eta(5)-C5Me5)(2) U(bipy) (8), diiminato compound (eta(5)-C5Me5)(2) U(N=CPh2)(2) (9) and the metallacyclopentatrienes (eta(5)-C5Me5)(2) U[te-C-4(R)(2)] (R = Ph (10), Me3Si (11)), respectively. Furthermore, compound 2 may also straightforwardly react with terminal alkynes and a variety of heterounsaturated (organic) molecules such as CS2, isothiocyanates, imines, diazenes, carbodiimides, nitriles, isonitriles, and organic azides. For instance, on treatment with phenylacetylene (PhC CH) the dialkynyl uranium complex (eta(5)-C5Me5)(2) U(C2Ph)(2) (OPMe3) (12) is formed, whereas CS2 and PhNCS furnish the carbodithioates (eta(5)-C5Me5)(2) U[SC(=P-2,4,6-Bu3C6H2)S](OPMe3) (13) and (eta(5)-C5Me5)(2) U[SC(=--NPh)S](OPMe3) (14), respectively. In the reaction of the secondary aldimine PhCH= NPh or the diazene PhN=NPh and 2 the uranium(IV) imido complex (q(5)-O5Me5)(2) U(=NPh)(OPMe3) (15) is isolated, which is in contrast to its reactivity with the primary ketimine 9-(C12H g )C=NH and the carbodiimides (RN=)(2)C, yielding the diiminato uranium(VI) complex (eta(5)-C5Me5)(2) U[N=C(C12H8)](2) (16) and the four-membered uranaheterocycles (eta(5)-C5Me5)(2) U[N(R)C(=P-2,4,6-(Bu3C6H2)-Bu-t)N(R)] (R = C6H11 (17), Pr (18)), respectively. Furthermore, treatment of 2 with nitriles RCN affords the imido uranium(IV) complexes (eta(5)-C5Me5)(2) U[=NC(=P-2,4,6-(Bu3C6H2)-Bu-t)R](OPMe3) (R = C6H11(19), Me3C (20)), whereas isonitriles RNC furnish the metallaaziridines (eta(5)-C5Me5)(2) U[C(=P-2,4,6-(Bu3C6H2)-Bu-t)N(R)1(OPMe3) (R = C6H11 (21), 2,6-Me2Ph (22)). However, in the reaction with organic azides RCN3, complex 2 yields the imido uranium(IV) complexes (eta(5)-C5Me5)(2) U(= NR)(OPMe3) (R = Ph3C (23), p-tolyl (24)) as a result of 3,3-Me-2-5,7-(Bu2C8H5P)-Bu-t (7) formation and N-2 release. The new compounds 12-24 were characterized by various spectroscopic techniques, including single-crystal X-ray diffraction analyses. Furthermore, with complex 2 in hand a comparison between the reactivity of uranium phosphinidenes differing in the steric bulk of its cyclopentadienyl ligands and the effects of a Lewis base (OPMe3) adduct was undertaken.
引用
收藏
页码:4085 / 4101
页数:17
相关论文
共 113 条
[1]   Nucleophilic Phosphinidene Complexes: Access and Applicability [J].
Aktas, Halil ;
Slootweg, J. Chris ;
Lammertsma, Koop .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (12) :2102-2113
[2]   N-Heterocyclic Carbene Functionalized Group 7-9 Transition Metal Phosphinidene Complexes [J].
Aktas, Halil ;
Slootweg, J. Chris ;
Ehlers, Andreas W. ;
Lutz, Martin ;
Spek, Anthony L. ;
Lammertsma, Koop .
ORGANOMETALLICS, 2009, 28 (17) :5166-5172
[3]   N-Heterocyclic Carbene-Functionalized Ruthenium Phosphinidenes: What a Difference a Twist Makes [J].
Aktas, Halil ;
Slootweg, J. Chris ;
Schakel, Marius ;
Ehlers, Andreas W. ;
Lutz, Martin ;
Spek, Anthony L. ;
Lammertsma, Koop .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (19) :6666-+
[4]   Recent advances in organothorium and organouranium catalysis [J].
Andrea, Tamer ;
Eisen, Moris S. .
CHEMICAL SOCIETY REVIEWS, 2008, 37 (03) :550-567
[5]   Matrix Infrared Spectra and Quantum Chemical Calculations of Ti, Zr, and Hf Dihydride Phosphinidene and Arsinidene Molecules [J].
Andrews, Lester ;
Cho, Han-Gook .
INORGANIC CHEMISTRY, 2016, 55 (17) :8786-8793
[6]  
[Anonymous], 1988, Metal-Ligand Multiple Bonds
[7]   Preparation of actinide phosphinidene complexes: Steric control of reactivity [J].
Arney, DSJ ;
Schnabel, RC ;
Scott, BC ;
Burns, CJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (28) :6780-6781
[8]   Remarkably stable titanium complexes containing terminal alkylidene, phosphinidene, and imide functionalities [J].
Bailey, BC ;
Huffman, JC ;
Mindiola, DJ ;
Weng, W ;
Ozerov, OV .
ORGANOMETALLICS, 2005, 24 (07) :1390-1393
[9]   Organoactinides in catalysis [J].
Barnea, Eyal ;
Eisen, Moris S. .
COORDINATION CHEMISTRY REVIEWS, 2006, 250 (7-8) :855-899
[10]   Single but stronger UO, double but weaker UNMe bonds:: The tale told by Cp2UO and Cp2UNR [J].
Barros, Noemi ;
Maynau, Daniel ;
Maron, Laurent ;
Eisenstein, Odile ;
Zi, Guofu ;
Andersen, Richard A. .
ORGANOMETALLICS, 2007, 26 (20) :5059-5065