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The reactions of [CpMn(CO) 2 (NO)]BF 4  or CpFe(CO) 2 Cl with PPh 2 NHR (R = Ph, PPh 2 ) lead to the salts [CpML(CO)PPh 2 NHR]X with monodentate aminophosphine ligands. In the case of R = PPh 2  (= dppa) the complexes [CpML(dppa)]X with bidentate dppa are also formed. The salt [CpFe(CO)(dppa)]Cl can be deprotonated to give the neutral complex CpFe(CO){(PPh 2 ) 2 N)} with the diphosphinoamide ligand, which can be N-alkylated by Mel to afford [CpFe(CO){(PPh 2 ) 2 NMe}]I. The complex [CpMn(NO)(dppa)]BF 4  undergoes a P-N cleavage reaction by the solvent methanol to form [CpMn(NO)(PPh 2 NH 2 )(PPh 2 OMe)]BF 4 . The non-chelated complexes [CpFe(CO) 2 PPh 2 NHR]Cl are deprotonated by DBU to give the neutral ferrioiminophosphoranes CpFe(CO) 2 PPh2 = NR. For R = PPh2 photolysis leads to CO-elimination and to CpFe(CO)(PPh 2 NPPh 2 ). CpFe(CO) 2 PPh 2 NPPh 2  can be alkylated by Mel or metallated by CpFe(CO) 2 Cl to form [CpFe(CO) 2 PPh 2 NPPh 2 Me]I or [CpFe(CO) 2 PPh 2 NPPh 2 (CO) 2 FeCp]Cl, respectively. Oxidation of CpFe(CO) 2 PPh 2 NPPh 2  is possible by (SiMe 3 ) 2 O 2 , sulfur, or selenium to lead to the neutral complexes CpFe(CO) 2 PPh 2 =NPPh 2  = E (E = O, S, Se) with a heterodiene system. The IR and NMR spectra of all species as well as the X-ray structures of the complexes [CpFe(CO)dppa]Cl, [CpMn(NO)dppa]BF 4  and [CpMn(NO)(PPh 2 NH 2 )(PPh 2 OMe)]BF 4  are reported and discussed.

zeitschrift für naturforschung b

Dppa als Komplexligand: Metall-Koordination und P-N-Spaltung in Komplexen des Typs [CpM(L)dppa]X (M = Fe, Mn; L = CO, NO) / Dppa as a Ligand: Metal Coordination and P-N Cleavage in Complexes of the Type [CpM(L)dppa]X (M = Fe, Mn; L = CO, NO)