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Darstellung and Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen. LXVIII. Phosphidomanganate als Bausteine zur Synthese von Phosphamanganacyclopropanen mit Carben- und Phosphiniden einheiten
Lindner, Ekkehard,Ossig, Elke,Darmuth, Monika
, p. 107 - 118 (2007/10/02)
The phosphidomanganates Li2(OC)4MnPR21> (3a-c) (R1=Ph (a), Cy (b), i-Pr (c)) are obttained by double deprotonation of HMn(CO)4PR21H (2a-c) with n-BuLi.Replacement of CO in HMn(CO)5 (1) by the phosphanes HPR21 affords 2a-c.The phosphamanganacyclopropanes (4a,b, 5a,b) (R2=Me (4), Ph (5)) and diphosphamanganacyclopropanes (OC)4MnPR21PR3, (6a, 7c, 8a,b and 9a-c) (R3=2,4,6-(t-Bu)3C6H2 (6), Ph (7), Cy (8), t-Bu (9)) are accessible by the action of the geminal dihalides R2CHCl2 and dichloroorganylpdhosphanes R3PCl2, respectively, on the phosphidomanganates 3a-c.The kinetic stability of 6-9 depends on the size of the substituents R1 and R3.The position of v(PP) in the IR spectra and the 1J(PP) coupling constants in the 31P-NMR spectra of 6-9 indicate a significant PP-? bonding character.
