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[1′-(Diphenylphosphino)ferrocenyl]methylamine ( 1 ) reacts with Ph 2 PH/(CH 2 O) x or [Ph 2 P(CH 2 OH) 2 ]Cl to give mixtures of Ph 2 PfcCH 2 NHCH 2 PPh 2 and Ph 2 PfcCH 2 N(CH 2 PPh 2 ) 2 in which the triphosphine dominates (fc = ferrocene-1,1′-diyl). To avoid unwanted two-fold phosphinomethylation, the amine group in 1 was alkylated. As expected, the reaction of the N -methyl analogue Ph 2 PfcCH 2 NHMe ( 5 ), obtained by reductive methylation of the aldehyde Ph 2 PfcCHO, with [Ph 2 P(CH 2 OH) 2 ]Cl, only led to the diphosphine Ph 2 PfcCH 2 N(Me)CH 2 PPh 2 ( 6 ). The diphosphine was structurally characterized and further reacted with [PdCl 2 (MeCN) 2 ] and [PdCl(Me)(cod)] (cod = η 2 :η 2 -cycloocta-1,5-diene), affording the respective trans -chelate complexes [PdCl(X){Ph 2 PfcCH 2 N(Me)CH 2 PPh 2 -κ 2 P , P ′}] ( 7a : X = Cl; 7b : X = Me), which were also structurally authenticated by X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

{[Tris(hydroxymethyl)methylamino]carbonyl}ferrocene ( 1 ) reacts with phosphorus(III) chloride in the presence of pyridine or triethylamine to afford a ferrocenyl-substituted bicyclic phosphite, {[(2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl)amino]carbonyl}ferrocene ( 2 ), in a moderate yield. (4,5-Dihydro-4,4-bis(chloromethyl)-2-oxazolyl)ferrocene ( 3 ) is found to be formed in some experiments as a minor side-product, resulting presumably via halogenation of 1 and base-induced cyclization of an intermediate chloromethyl derivative. The reaction of 2 with [W(CO) 4 (cod)] (cod = cycloocta-1,5-diene) at elevated temperature produces bis-phosphite complex cis -[W(CO) 4 ( 2 -κ P ) 2 ] ( 4 ) as the major product. All newly prepared compounds have been characterized by spectroscopic methods (IR, NMR and mass spectrometry) and elemental analysis. The crystal structures of 2 , 3 ·1/2H 2 O and 4 ·Me 2 CO·H 2 O were determined by single-crystal X-ray diffraction and the redox behaviour of phosphite 2 and the W(0) complex 4 was studied by cyclic voltammetry. [ABSTRACT FROM AUTHOR]