Molybdenum Carbonyl Complexes Bearing PN Ligands Based on 2‐Aminopyridine

Abstract

Molybdenum complexes of the general formula Mo(PN)(CO)4 containing both achiral and chiral phosphorus‐nitrogen donor bidentate ligands based on 2‐aminopyridine were prepared and characterized by their NMR and IR spectra. The oxidative addition of allyl bromide to Mo(PN)(CO)4 was studied with PN = N‐(diisopropylphosphanyl)‐2‐aminopyridine (PN‐iPr). X‐ray structures of representative compounds were determined. The mechanism of the oxidative addition of allyl bromide to Mo(PN‐iPr)(CO)4 was analyzed by DFT/B3LYP calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Hemilability of P(X)N-type ligands (X = O, N–H): rollover cyclometalation and benzene C–H activation from (P(X)N)PtMe2complexes

“…The chemistry of the related bifunctional P(N-H)N ligand on platinum was also examined. The tBu P(N-H)N ligand ( tBu P(N-H)N = (di-tert-butylphosphino)-2-aminopyridine) 32 was combined with [PtMe 2 (SMe 2 )] 2 15 in toluene at room temperature to generate ( tBu P(N-H)N)PtMe 2 (3). Complex 3 was characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography.…”

“…13 Synthesis of tBu P(N-H)N. The preparation of tBu P(N-H)N is based on the reported synthesis of a related molecule. 32 A Schlenk flask was charged with 2-aminopyridine (1.56 g, 16.6 mmol) in THF (40 mL). The solution was cooled in a dry ice/acetone bath and n-butyllithium (∼2.5 M hexanes, 7.8 mL, 20 mmol) was added by syringe.…”

Bis{2-[(diisopropylphosphanyl)amino]pyridine-κ2N1,P}copper(I) hexafluoridophosphate

“…Some transition metal complexes of these ligands, mainly with diphenylphosphane moieties, are catalytically active and have been applied for carbonylation of olefins and other transformations (Aguirre et al, 2007;Benito-Garagorri, Wiedermann et al, 2007). In continuation of earlier work on Ni(II), Pd(II), and Mo(0/II)-complexes of such ligands Standfest-Hauser et al, 2009) we recently focused on Cu(I) complexes and report here the synthesis and crystal structure of the title compound [Cu(PN-iPr) 2 ]PF 6 . A view of the asymmetric unit is shown in Fig.…”

“…For the synthesis and crystal structures of PN-complexes [PN are 2-(phosphanylamino)pyridines], see: Aucott et al (2000); ; Standfest-Hauser et al (2009). For applications of PN-complexes in catalysis, see: Aguirre et al (2007); Benito-Garagorri, Wiedermann et al (2007).…”

Synthesis, Characterization and Ab Initio Calculations of Aminophosphine Derived From 4-Benzylpiperidine, its Chalcogenide Derivatives and Molybdenum(0) Complex

“…5 exhibits four intense CO stretching bands in the carbonyl region (1771-2009 cm −1 ) due to 2A 1 +B 1 +B 2 modes as expected for C 2v symmetry and in agreement with cis-[Mo(CO) 4 L 2 ]. 5,21,22 In some cis-[Mo(CO) 4 …”