| Inorganica Chimica Acta | onAcademic

来自 : www.onacademic.com/detail/jour 发布时间：2021-03-25

Author: Gusev, Oleg V. Ievlev, Mikhail A. Lyssenko, Konstantin A. Petrovskii, Pavel V. Ustynyuk, Nikolai A. et. al.

Journal: Inorganica Chimica Acta

Issue Date: 1998

Abstract(summary):
The reaction of RuCl3(H2O)x with C5Me4CF3H in refluxing EtOH gives [Ru2( 5-C5Me4CF3)2Cl2( -Cl)2] (2) in 44%yield. Dimer 2 is antiferromagnetic ( 2J = 200 cm 1). The crystal structures of 2 (rhombohedral system, R space group, Z = 9, R = 0.0589) and [Rh2( 5-C5Me4CF3)2Cl2( -Cl)2] (3) (rhombohedral system, R space group, Z = 9, R = 0.0641) were solved; both complexes have dimeric structures with a trans arrangement of the 5-C5Me4CF3 rings. Comparison of the geometry of 2 and 3 with those of the corresponding 5-C5Me5 complexes shows that lowering the ring symmetry causes significant distortion of the M2( -Cl)2 moiety. The analysis of the MCl3 fragment conformations in 2 and 3 and in the 5-C5Me5 analogues shows that they are correlated with the M-M distances. The Cl atoms are displaced by Br on reaction of 2 with KBr in MeOH to give the diamagnetic dimer [Ru2( 5-C5Me4CF3)2Br2( -Br)2] (4). Complex 2 reacts with O2 in CH2Cl2 solution at ambient temperature to form a mixture of isomeric 6-fulvene dimers [Ru2( 6-C5Me3CF3

Page: 249-256


Dimer 2 is antiferromagnetic (− 2J = 200 cm−1). The crystal structures of 2 (rhombohedral system, R space group, Z = 9, R = 0.0589) ...onAcademic ；Science；Technology；Medicine；researchThe reaction of RuCl₃(H₂O)_<i>x</i> with C₅Me₄CF₃H in refluxing EtOH gives [Ru₂(&#951;<SUP>5</SUP>-C₅Me₄CF₃)₂Cl₂(&#956;-Cl)₂] (<b>2</b>) in 44%yield. Dimer <b>2</b> is antiferromagnetic (&minus; 2<i>J</i> = 200 cm<SUP>&minus;1</SUP>). The crystal structures of <b>2</b> (rhombohedral system, <i>R</i> space group, <i>Z</i> = 9, <i>R</i> = 0.0589) and [Rh₂(&#951;<SUP>5</SUP>-C₅Me₄CF₃)₂Cl₂(&#956;-Cl)₂] (<b>3</b>) (rhombohedral system, <i>R</i> space group, <i>Z</i> = 9, <i>R</i> = 0.0641) were solved; both complexes have dimeric structures with a <i>trans</i> arrangement of the &#951;<SUP>5</SUP>-C₅Me₄CF₃ rings. Comparison of the geometry of <b>2</b> and <b>3</b> with those of the corresponding &#951;<SUP>5</SUP>-C₅Me₅ complexes shows that lowering the ring symmetry causes significant distortion of the M₂(&#956;-Cl)₂ moiety. The analysis of the MCl₃ fragment conformations in <b>2</b> and <b>3</b> and in the &#951;<SUP>5</SUP>-C₅Me₅ analogues shows that they are correlated with the M-M distances. The Cl atoms are displaced by Br on reaction of <b>2</b> with KBr in MeOH to give the diamagnetic dimer [Ru₂(&#951;<SUP>5</SUP>-C₅Me₄CF₃)₂Br₂(&#956;-Br)₂] (<b>4</b>). Complex <b>2</b> reacts with O₂ in CH₂Cl₂ solution at ambient temperature to form a mixture of isomeric &#951;<SUP>6</SUP>-fulvene dimers [Ru₂(&#951;<SUP>6</SUP>-C₅Me₃CF<sub>3