Unusual ''cation-like'' zirconocene hydrosilyl complex. Silylium ligand or a nonclassically bonded Si-H?

被引:39
作者
Dioumaev, VK [1 ]
Harrod, JF [1 ]
机构
[1] MCGILL UNIV,DEPT CHEM,MONTREAL,PQ H3A 2K6,CANADA
关键词
D O I
10.1021/om960254m
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The novel zirconocene complexes [Cp'Zr-2(mu-H)(SiHR)](2+)(2)[BR'(n)(C6F5)(4-n)](2-)(2) (Cp'=Cp, MeCp, Me(5)Cp; R=Ph or PhCH(2); R'=Bu or H) were isolated from silane dehydropolymerization reaction mixtures catalyzed by Cp'2ZrCl2/2BuLi/B(C6F5)(3) or by [Cp(2)'Zr(mu-H)H](2)/2B(C6F5)(3) combination catalysts. A total structure analysis of these compounds, performed by multinuclear, multidimensional NMR spectroscopy, shows that each zirconocene fragment bears a positive charge, which is delocalized between the metal center and hydrosilane ligand.
引用
收藏
页码:3859 / 3867
页数:9
相关论文
共 80 条
[41]   PERFLUOROPHENYL DERIVATIVES OF THE ELEMENTS .1. TRIS(PENTAFLUOROPHENYL)BORON [J].
MASSEY, AG ;
PARK, AJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1964, 2 (03) :245-250
[42]  
Mislow K., 1967, TOP STEREOCHEM, V1, P1, DOI DOI 10.1002/9780470147108.CH1
[43]   NOVEL TRANS-ETA(2)-ALKYNE COMPLEXES OF TITANOCENE WITH STRONG SI-H-TI INTERACTIONS - SYNTHESIS, SPECTRAL CHARACTERISTICS, AND X-RAY CRYSTAL-STRUCTURE [J].
OHFF, A ;
KOSSE, P ;
BAUMANN, W ;
TILLACK, A ;
KEMPE, R ;
GORLS, H ;
BURLAKOV, VV ;
ROSENTHAL, U .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (41) :10399-10400
[44]   ORGANO-METALLIC CHEMISTRY .19. CORRELATION OF SI-29 TO C-13 NMR CHEMICAL-SHIFTS IN ANALOGOUS COMPOUNDS - APPLICATION IN ATTEMPTED PREPARATION OF SILICENIUM IONS [J].
OLAH, GA ;
FIELD, LD .
ORGANOMETALLICS, 1982, 1 (11) :1485-1487
[45]  
OLAH GA, 1994, SCIENCE, V263, P983
[46]   ORGANOMETALLIC CHEMISTRY .24. CONTINUED SEARCH FOR ELUSIVE PERSISTENT TRIVALENT ORGANOSILYL CATIONS - THE CLAIMED TRIMETHYLSILYL CATION REVISITED - ATTEMPTED PREPARATION OF CYCLIC AND HALOGEN-BRIDGED ORGANOSILICENIUM IONS [J].
OLAH, GA ;
RASUL, G ;
HEILIGER, L ;
BAUSCH, J ;
PRAKASH, GKS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (20) :7737-7742
[47]   ORGANOMETALLIC CHEMISTRY .23. THE COVALENT NATURE OF TRIMETHYLSILYL PERCHLORATE AND OBSERVATION OF POLARIZED FLUOROTRIMETHYLSILANE-ANTIMONY PENTAFLUORIDE COMPLEXES BASED ON SI-29 NMR-STUDIES - DIFFICULTIES IN OBSERVING LONG-LIVED PERSISTENT TRIALKYLSILICENIUM IONS [J].
OLAH, GA ;
HEILIGER, L ;
LI, XY ;
PRAKASH, GKS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (16) :5991-5995
[48]   PROPERTIES OF R(3)SIX COMPOUNDS AND R(3)SI(+) IONS - DO SILYLIUM IONS EXIST IN SOLUTION [J].
OLSSON, L ;
OTTOSSON, CH ;
CREMER, D .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (28) :7460-7479
[49]   EVIDENCE FOR THE EXISTENCE OF SILYLIUM CATIONS IN CONDENSED PHASES [J].
OLSSON, L ;
CREMER, D .
CHEMICAL PHYSICS LETTERS, 1993, 215 (05) :433-443
[50]  
PAULING L, 1994, SCIENCE, V263, P983, DOI 10.1126/science.263.5149.983