148422-19-9Relevant academic research and scientific papers
Behavior of the bis(chelate) complex [Rh(P O)2][BPh4] toward acyl halides and carbon monoxide. Investigation of a reversible alkyl migration
Lindner, Ekkehard,Wang, Qinyan,Mayer, Hermann August,Fawzi, Riad,Steimann, Manfred
, p. 1865 - 1870 (2008/10/08)
The bis(chelate) complex [Rh(P O)2][BPh4] (2; P O = η272(O,P)-chelated (C6H11)2PCH2CH2-OCH 3 ligand) reacts with acyl chlorides RC(O)Cl to give the acyl complexes [Rh(P O)2C(O)-RCl][BPh4] (4a-e; R = CH3 (a), C2H5 (b), i-C3H7 (c), Ph (d), C2H4Ph (e)). The structure of 4c, showing a distorted-octahedral configuration, was elucidated by an X-ray structural analysis. 4c crystallizes in the monoclinic space group P2/n with Z = 4. The cell dimensions are a = 21.881(4) A?, b = 10.303(2) A?, c = 26.516(5) A?, and β = 100.91(3)°. The reductive-elimination process of 4a proceeds via a reverse methyl migration to give 6a, followed by elimination of CH3Cl from 6a to form the carbonylrhodium(I) complex [Rh(CO)(P～O)(P O)][BPh4] (8;P～O = η1(P)-coordinated (C6H11)2PCH2CH2OCH 3 ligand). [ClRh(P～O)2(CO)] (9) is observed as the final product. Both Rh-O bonds in 2 are cleaved by 5-bar pressure of carbon monoxide, resulting in the formation of the tricarbonylrhodium(I) complex [Rh(P～O)2(CO)3][BPh4] (3). Upon bubbling argon through a CH2Cl2 solution of 3, [(OC)2Rh(P～O)2][BPh4] (cis-5 or trans-7) is favored compared to the monocarbonyl species 8.
