The donor ability of constrained bicyclic aminophosphane ligands P(OCH2CH2)2N (la) and P(OCMe2CH2)2N (lb) has been evaluated and compared with that of their acyclic analogue (EtO)2PNMe2 (lc) toward a series of CpMo(CO)3X derivatives (X = H, Cl, CH3). A CO group in CpMo(CO)3Cl is readily substituted at room temperature; further substitution requires photochemical activation. Coordination always occurs through P. The i'(CO) frequencies of the adducts indicate a higher 7r-accepting character for the bicyclic ligands than for the nonconstrained analogue. Gaseous HC1 provokes the quaternization of the nitrogen site in HCpMo(CO)2 (lb), which thus displays definite basicity while retaining the P-N bond; in contrast, HC1 cleaves the P-N bond of the adduct of the noncyclic lc. The first stable compound with a protonated P-bound nitrogen could thus be isolated and was fully characterized.
Der Aminophosphin‐Ligand im Mo‐Komplex (I) wird durch gasförmiges HCl am N‐Atom ohne Bindungsspaltung unter Bildung des stabilen, jedoch sauerstoffempfindlichen Phosphorammonium‐Salzes (IIa) protoniert.
Die Donatorfähigkeit der beiden aufgezeichneten bicyclischen Aminophosphine gegenüber den Cyclopentadienyltricarbonyl‐Mo‐Komplexen (II), (IV) und dem analogen Hydrid wird untersucht und mit der des acyclischen (EtO)2PNMe2 verglichen.
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