Versatile Conversion of N-Heterocyclic Silylene to Silyl Metal Compounds by Insertion of Divalent Silicon into Metal-Carbon and Metal-Hydrogen Bonds

被引:30
作者
Xiong, Yun [1 ]
Yao, Shenglai [1 ]
Driess, Matthias [1 ]
机构
[1] Tech Univ Berlin, Inst Chem Metalorgan & Inorgan Mat, D-10623 Berlin, Germany
关键词
dimethyl zinc; lithium; metal silanide; metalation; trimethylaluminum; YLIDE-LIKE SILYLENE; X-RAY CRYSTAL; STABLE SILYLENE; REACTIVITY; ACTIVATION; DERIVATIVES; COMPLEXES; CHEMISTRY; ADDUCTS; LIGAND;
D O I
10.1002/chem.201103656
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The facile one-pot reaction of the stable N-heterocyclic silylene LSi: 1 (L?(ArN)C(?CH2) CH?C(Me)(NAr), Ar=2,6-iPr2C6H3) with Me2Zn, Me3Al, H3Al-NMe3, and MeLi has been investigated. The silicon(II) atom in 1 is capable of insertion into the corresponding M?C and Al?H bonds under very mild reaction conditions. Thus, Me2Zn furnishes the bis(silyl) zinc complex LSi(Me)ZnSi(Me)L 2 as the sole product, irrespective of the molar ratio of the starting materials applied. Moreover, the reactions of 1 with Me3Al, H3Al-NMe3, and MeLi lead directly to the 1,1-addition products LSi(Me)(Al(thf)Me2) 3, LSi(H)(AlH2(NMe3)) 4, and LSi(Me)Li(thf)3 5, respectively. All new compounds 25 were fully characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single-crystal X-ray diffraction analyses.
引用
收藏
页码:3316 / 3320
页数:5
相关论文
共 48 条
[1]  
[Anonymous], 2007, ANGEW CHEM
[2]  
[Anonymous], 1997, SHELX 97 PROGRAM CRY
[3]   N-Heterocyclic Carbene Analogues with Low-Valent Group 13 and Group 14 Elements: Syntheses, Structures, and Reactivities of a New Generation of Multitalented Ligands [J].
Asay, Matthew ;
Jones, Cameron ;
Driess, Matthias .
CHEMICAL REVIEWS, 2011, 111 (02) :354-396
[4]   Silylzincation of carbon-carbon multiple bonds revisited [J].
Auer, G ;
Oestreich, M .
CHEMICAL COMMUNICATIONS, 2006, (03) :311-313
[5]   Reactions of Stable N-Heterocyclic Silylenes with Ketones and 3,5-Di-tert-butyl-o-benzoquinone [J].
Azhakar, Ramachandran ;
Ghadwal, Rajendra S. ;
Roesky, Herbert W. ;
Hey, Jakob ;
Stalke, Dietmar .
ORGANOMETALLICS, 2011, 30 (14) :3853-3858
[6]  
Belzner J, 1998, CHEM FUNCT, V2, P779, DOI 10.1002/0470857250.ch14
[7]   Reactions of a cyclotrisilane with Lewis acids -: formation of new cyclotrisilanes and siliconium ions [J].
Belzner, J ;
Ronneberger, V ;
Schär, D ;
Brönnecke, C ;
Herbst-Irmer, R ;
Noltemeyer, M .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 577 (02) :330-336
[8]   The stable silylene Si[(NCH2tBu)2C6H4-1,2]:: insertion into Li-C or Li-Si bonds of lithium alkyls LiR or [LiSi(SiMe3)3(THF)3] [R = Me, tBu or CH(SiMe3)2] [J].
Cai, XP ;
Gehrhus, B ;
Hitchcock, PB ;
Lappert, MF ;
Slootweg, JC .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 643 :272-277
[9]   THE X-RAY CRYSTAL-STRUCTURES OF THE MONONUCLEAR SILYLLITHIUM SPECIES LI(THF)(3)SIPH(3) AND LI(THF)(3)SI(SIME(3))(3) [J].
DIAS, HVR ;
OLMSTEAD, MM ;
RUHLANDTSENGE, K ;
POWER, PP .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1993, 462 (1-2) :1-6
[10]   A new type of N-heterocyclic silylene with ambivalent reactivity [J].
Driess, Matthias ;
Yao, Shenglai ;
Brym, Markus ;
van Wuellen, Christoph ;
Lentz, Dieter .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (30) :9628-9629