Mück Felix M, Baus Johannes A, Nutz Marco, Burschka Christian, Poater Jordi, Bickelhaupt F Matthias, Tacke Reinhold
Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84609.
VU University Amsterdam, Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling (ACMM), De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands).
Chemistry. 2015 Nov 9;21(46):16665-72. doi: 10.1002/chem.201501788. Epub 2015 Oct 1.
Activation of CO2 by the bis(amidinato)silylene 1 and the analogous bis(guanidinato)silylene 2 leads to the structurally analogous six-coordinate silicon(IV) complexes 4 (previous work) and 8, respectively, the first silicon compounds with a chelating carbonato ligand. Likewise, CS2 activation by silylene 1 affords the analogous six-coordinate silicon(IV) complex 10, the first silicon compound with a chelating trithiocarbonato ligand. CS2 activation by silylene 2, however, yields the five-coordinate silicon(IV) complex 13 with a carbon-bound CS2 (2-) ligand, which also represents an unprecedented coordination mode in silicon coordination chemistry. Treatment of the dinuclear silicon(IV) complexes 5 and 6 with CO2 also affords the six-coordinate carbonatosilicon(IV) complexes 4 and 8, respectively.
双（脒基）硅烯1和类似的双（胍基）硅烯2对CO₂的活化分别导致结构类似的六配位硅（IV）配合物4（先前的工作）和8，这是首批含有螯合碳酸根配体的硅化合物。同样，硅烯1对CS₂的活化产生了类似的六配位硅（IV）配合物10，这是首个含有螯合三硫代碳酸根配体的硅化合物。然而，硅烯2对CS₂的活化产生了具有碳键合CS₂（2-）配体的五配位硅（IV）配合物13，这在硅配位化学中也代表了一种前所未有的配位模式。用CO₂处理双核硅（IV）配合物5和6也分别得到了六配位的碳酸硅（IV）配合物4和8。
