Johnson Heather C, Weller Andrew S
Department of Chemistry, University of Oxford, Mansfield Road, Oxford, OX1 3TA (UK).
Angew Chem Int Ed Engl. 2015 Aug 24;54(35):10173-7. doi: 10.1002/anie.201504073. Epub 2015 Jul 3.
{Rh(xantphos)}-based phosphido dimers form by P-C activation of xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) in the presence of amine-boranes. These dimers are active dehydrocoupling catalysts, forming polymeric [H2 BNMeH]n from H3 B⋅NMeH2 and dimeric [H2 BNMe2 ]2 from H3 B⋅NMe2 H at low catalyst loadings (0.1 mol %). Mechanistic investigations support a dimeric active species, suggesting that bimetallic catalysis may be possible in amine-borane dehydropolymerization.
基于{Rh(xantphos)}的磷化物二聚体通过在胺硼烷存在下对呫吨膦（4,5-双（二苯基膦基）-9,9-二甲基呫吨）进行P-C活化而形成。这些二聚体是活性脱氢偶联催化剂，在低催化剂负载量（0.1 mol %）下，由H₃B⋅NMeH₂形成聚合的[H₂BNMeH]ₙ，由H₃B⋅NMe₂H形成二聚的[H₂BNMe₂]₂。机理研究支持二聚活性物种，表明在胺硼烷脱氢聚合中双金属催化可能是可行的。
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