92922-75-3Relevant academic research and scientific papers
Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, XXXVII. Investigations on the Reactivity and Decomposition of Unstable Oxaphosphamanganacyclopentanes
Lindner, Ekkehard,Broesamle, Andreas
, p. 2730 - 2744 (2007/10/02)
The thermally labile five-membered metallacycles (OC)4Mn-(PPh2OCHR1)-CHR2 (3a-c) are obtained by reductive cycloelimination of (OC)4BrMnPPh2OCHR1CHR2Cl (2a-c) with sodium amalgam at 0 deg C in ether.According to kinetic investigations the decomposition of 3a-c, which results in the formation of2 (4) and ethene or propene, respectively, follows a first-order rate law.The estimated activation parameters ΔH*, ΔS*, and ΔG* indicate decreasing stability within the series 3b > 3a > 3c.The action of Co or HBr on 3a generates the phosphane oxide complex (OC)5MnP(Ph)2O (5) and (OC)4BrMnPPh2OH (6), respectively.Sulfur dioxide is easily inserted into the Mn-C ?-bond of 3a-c with formation of the stable cyclic sulfinato-S complexes (OC)4Mn-(PPh2OCHR1CHR2)-SO2 (7a-c).
