Ou Xinrui, Kong Fanji, Quirion Kevin P, Webber Christopher K, Dickie Diane A, Ess Daniel H, Gunnoe T Brent
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States.
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84604, United States.
Organometallics. 2025 Aug 1;44(15):1639-1643. doi: 10.1021/acs.organomet.5c00187. eCollection 2025 Aug 11.
We report the synthesis of Rh-Sb complexes using high valent Sb ligands, QSbCl (, Q = 8-quinolinyl) and QSbF (), from the low valent Rh precursor [(CO)Rh-(μ-Cl)] to afford the complexes [(κ-QSbCl)-Rh-(CO)-Cl]-[(CO)RhCl] () and (κ-QSbF)-Rh-(CO)Cl (), respectively. The reaction of with [(CO)Rh-(μ-Cl)] results in the transfer of chloride from Sb to Rh to give the ion pair with a Rh-Sb bond for the cation that, according to computational analysis, has some covalent character. Replacing Sb-Cl with Sb-F bonds (, compound ) inhibited halide transfer and allowed formation of with a Rh→Sb interaction that has more Z-type character than the Rh-Sb bond for complex . Molecular orbital and localized orbital bonding analyses are consistent with the proposed Rh→Sb interaction of being more Z-type in character.
我们报道了使用高价锑配体QSbCl（Q = 8 - 喹啉基）和QSbF，从低价铑前体[(CO)Rh-(μ-Cl)]合成铑 - 锑配合物，分别得到配合物[(κ-QSbCl)-Rh-(CO)-Cl]-[(CO)RhCl]（）和(κ-QSbF)-Rh-(CO)Cl（）。与[(CO)Rh-(μ-Cl)]的反应导致氯离子从锑转移到铑，生成离子对，其阳离子具有铑 - 锑键，根据计算分析，该键具有一定的共价性质。用锑 - 氟键取代锑 - 氯键（，化合物）抑制了卤化物转移，并允许形成具有铑→锑相互作用的，该相互作用比配合物的铑 - 锑键具有更多的Z型特征。分子轨道和定域轨道键合分析与所提出的的铑→锑相互作用在性质上更具Z型一致。
