Koordinationschemie funktioneller Phosphine: Carbonyl- und Carbonyl(nitrosyl)wolfram-Derivate von 2-Diphenylphosphinoanilin und 2-Diphenylphosphinobenzoesaeure

Article abstract of DOI:10.1016/0022-328X(94)80193-2

Replacement of CO by monodentate phosphines PR3 in ^-, followed by treatment with Ph2PC6H4X-2 of the resulting anions ^-, afforded the mixed phosphine complexes (PR3 = PMe3, PBu3, PPh2Me and PPh3) 1a-1d (X = NH2) and 2a-2d (X = CO2H), respectively. ^- (3), prone to further transformation into 2-Ph2PC6H4NH2-2)> (4) after loss of Cl^-, resulted from initial interaction of ^- with Ph2PC6H4NH2-2.Except for minor quantities of (5), no well-defined nitrosyl products were accessible from reactions of tetracarbonyls 1 and 2 with NO⁺ salts.Such derivatives, viz., (6), by rapidly ejecting CO under formation of the more stable 2-Ph2PC6H4NH2-2)> (PR3 = PMe3: 7a; PPh2Me: 7b), 1-Ph2PC6H4NH2-2)(η²-Ph2PC6H4NH2-2)>> (A = SbF6: 8-SbF6; BF4: 8-BF4) and 2-Ph2PC6H4NH2-2)2> (9), could be synthesized via displacement reactions of loosely-coordinated ligands (FPF5^- and MeCN) by Ph2PC6H4NH2-2 from pre-formed nitrosyl species, e.g., and ⁺, respectively.The structure of the complexes , (1c), 2<2-Ph2PC6H4NH2-2)>2Cl2> ( 4*Cl ), 2-Ph2PC6H4NH2-2)> (7a), 1-Ph2PC6H4NH2-2)(η²-Ph2PC6H4NH2-2)> (8-SbF6, as an addition compound with 0.5Et2O and 0.5CH2Cl2), and 2-Ph2PC6H4NH2-2)2> (9, containing 1H2O of crystallization) have been determined by single-crystal X-ray diffraction studies.Key words: Phosphine; Tungsten; Carbonyl; Nitrosyl; X-ray diffraction