Aminoborane σ Complexes: Significance of Hydride Co-ligands in Dynamic Processes and Dehydrogenative Borylene Formation

被引：26
作者：
Addy, David A. [1 ]
Bates, Joshua I. [1 ]
Kelly, Michael J. [1 ]
Riddlestone, Ian M. [1 ]
Aldridge, Simon [1 ]
机构：
[1] Univ Oxford, Dept Chem, Inorgan Chem Lab, Oxford OX1 3QR, England
来源：
ORGANOMETALLICS | 2013年 / 32卷 / 06期
基金：
加拿大自然科学与工程研究理事会; 英国工程与自然科学研究理事会;
关键词：
AMINE-BORANES; RUTHENIUM COMPLEX; BOND METATHESIS; X-RAY; METAL; COORDINATION; BORON; IRIDIUM; HYDROBORATION; CHEMISTRY;
D O I：
10.1021/om400040q
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Systems of the type [(p-cym)Ru(PR3)(H)-((H2BNPr2)-Pr-i)](+) (R = Cy, Ph) can be synthesized from (p-cym)Ru-(PR3)Cl-2 and (H2BNPr2)-Pr-i/Na[BAr4f] and are best formulated as (hydrido)rutheniurn kappa(1)-aminoborane complexes. VT-NMR measurements have been used to probe the sigma-bond metathesis process leading to Ru-H/H-B exchange, yielding an activation barrier of Delta G(double dagger) = 7.5 kcal mol(-1) at 161 K. Moreover, in contrast to the case for related non-hydride-containing systems, reactivity toward alkenes constitutes a viable route to a metal borylene complex via sacrificial hydrogenation.
引用
收藏
页码：1583 / 1586
页数：4
相关论文
共 54 条
  • [1] NMR: A good tool to ascertain σ-silane or σ-borane formulations?
    Alcaraz, Gilles
    Sabo-Etienne, Sylviane
    [J]. COORDINATION CHEMISTRY REVIEWS, 2008, 252 (21-22) : 2395 - 2409
  • [2] A terminal borylene ruthenium complex: From B-H activation to reversible hydrogen release
    Alcaraz, Gilles
    Helmstedt, Ulrike
    Clot, Eric
    Vendier, Laure
    Sabo-Etienne, Sylviane
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (39) : 12878 - +
  • [3] Mesitylborane as a bis(σ-B-H) ligand:: An unprecedented bonding mode to a metal center
    Alcaraz, Gilles
    Clot, Eric
    Helmstedt, Ulrike
    Vendier, Laure
    Sabo-Etienne, Sylviane
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (28) : 8704 - +
  • [4] Ruthenium, Rhodium, and Iridium Bis(σ-B-H) Diisopropylaminoborane Complexes
    Alcaraz, Gilles
    Chaplin, Adrian B.
    Stevens, Charlotte J.
    Clot, Eric
    Vendier, Laure
    Weller, Andrew S.
    Sabo-Etienne, Sylviane
    [J]. ORGANOMETALLICS, 2010, 29 (21) : 5591 - 5595
  • [5] Coordination and Dehydrogenation of Amine-Boranes at Metal Centers
    Alcaraz, Gilles
    Sabo-Etienne, Sylviane
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (40) : 7170 - 7179
  • [6] Ruthenium Bis(σ-B-H) Aminoborane Complexes from Dehydrogenation of Amine-Boranes: Trapping of H2B-NH2
    Alcaraz, Gilles
    Vendier, Laure
    Clot, Eric
    Sabo-Etienne, Sylviane
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (05) : 918 - 920
  • [7] Bis σ-Bond Dihydrogen and Borane Ruthenium Complexes: Bonding Nature, Catalytic Applications, and Reversible Hydrogen Release
    Alcaraz, Gilles
    Grellier, Mary
    Sabo-Etienne, Sylviane
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (10) : 1640 - 1649
  • [8] Chemistry of metal - boron double bonds
    Aldridge, Simon
    Kays, Deborah L.
    [J]. MAIN GROUP CHEMISTRY, 2007, 5 (04) : 223 - 249
  • [9] Group VI metal aminoborylene complex-catalyzed demercuration reactions of bis(alkynyl)mercurials
    Apostolico, Leonardo
    Braunschweig, Holger
    Crawford, Andrew G.
    Herbst, Thomas
    Rais, Daniela
    [J]. CHEMICAL COMMUNICATIONS, 2008, (04) : 497 - 498
  • [10] REACTIVITY OF RUTHENIUM TRIHYDRIDES WITH BRONSTED AND LEWIS-ACIDS - X-RAY CRYSTAL-STRUCTURES OF (CP-STAR-RU[C6H9P(C6H11)2])BF4 AND ((CP-STAR-RUH[P(C6H11)3])(MU-H)2CU(MU-CL))2 - EVIDENCE FOR EXCHANGE COUPLING BETWEEN 2 HYDROGEN-ATOMS
    ARLIGUIE, T
    CHAUDRET, B
    JALON, FA
    OTERO, A
    LOPEZ, JA
    LAHOZ, FJ
    [J]. ORGANOMETALLICS, 1991, 10 (06) : 1888 - 1896
123456