Noncoordinating anions - Fact or fiction? A survey of likely candidates

被引:966
作者
Krossing, I [1 ]
Raabe, I [1 ]
机构
[1] Univ Karlsruhe, D-76128 Karlsruhe, Germany
关键词
alkoxymetallates; aluminates; anions; carboranes; Lewis acids;
D O I
10.1002/anie.200300620
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Is there anything resembling a truly noncoordinating anion? Would it not be great to be able to prepare any crazy, beautiful, or simply useful cationic species that one has in mind, or has detected by mass spectroscopy? In condensed phases the target cation has to be partnered with a suitable counteranion. This is the moment when difficulties arise and many wonderful ideas end in the sink owing to coordination or decomposition of the anion. However, maybe these counteranion problems can be overcome by one of the new weakly coordinating anions (WCAs). Herein is an overview on the available candidates in the quest for the least coordinating anion and a summary of new applications, available starting materials, and general strategies to introduce a WCA into a system. Some of the unusual properties of WCA salts such as high solubility in low dielectric media, pseudo gas-phase conditions in condensed phases, and the stabilization of weakly bound and low-charged complexes are rationalized on thermodynamic grounds. Limits of the WCAs, that is, anion coordination and decomposition, are shown and a quantum chemical analysis of all types of WCAs is presented which allows the choice of a particular WCA to be based on quantative data from a wide range of different anions.
引用
收藏
页码:2066 / 2090
页数:25
相关论文
共 292 条
  • [1] Extending the coordination chemistry of molecular P4S3:: The polymeric Ag(P4S3)+ and Ag(P4S3)2+ cations
    Adolf, A
    Gonsior, M
    Krossing, I
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (24) : 7111 - 7116
  • [2] [Anonymous], ANGEW CHEM
  • [3] [Anonymous], CRC HDB CHEM PHYS
  • [4] [Anonymous], CHEMTRACTS INORG CHE
  • [5] LiAl(OC(Ph)(CF3)(2))(4): A hydrocarbon-soluble catalyst for carbon-carbon bond-forming reactions
    Barbarich, TJ
    Handy, ST
    Miller, SM
    Anderson, OP
    Grieco, PA
    Strauss, SH
    [J]. ORGANOMETALLICS, 1996, 15 (18) : 3776 - 3778
  • [6] Coordination of the new weakly coordinating anions Al(OCH(CF3)2)4-, Al(OC(CH3)(CF3)2)4-, and Al(OC(Ph)(CF3)2)4- to the monovalent metal ions Li+ and Tl+
    Barbarich, TJ
    Miller, SM
    Anderson, OP
    Strauss, SH
    [J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1998, 128 (1-3) : 289 - 331
  • [7] Bardin VV, 2002, Z ANORG ALLG CHEM, V628, P883, DOI 10.1002/1521-3749(200205)628:4<883::AID-ZAAC883>3.0.CO
  • [8] 2-A
  • [9] Bardin VV, 2002, MAIN GROUP MET CHEM, V25, P589
  • [10] Use of medium effects to tune the ΔE1/2 values of bimetallic and oligometallic compounds
    Barrière, F
    Camire, N
    Geiger, WE
    Mueller-Westerhoff, UT
    Sanders, R
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (25) : 7262 - 7263