Synthesis and Reactivity of Group 6 and 10 Complexes of the Bis(dialkylaminophosphanyl)imineiPrN=C[CH2P(NiPr2)2]2

Abstract

The coordination behaviour of the readily prepared, potentially ambidentate, bis(α,αЈ-phosphanyl)imine (iPr 2 N) 2 -PCH 2 C(=NiPr)CH 2 P(NiPr 2 ) 2 (1, PNP) has been investigated. Treatment of palladium(II), platinum(II), chromium(0), and molybdenum(0) sources with ligand 1 afforded complexes in which 1 was coordinated solely in a bidentate P,N-chelating

Diphenylphosphino(phenyl pyridin-2-yl methylene)amine palladium(II) complexes: Chemoselective alkene hydrocarboxylation initiators

“…The plane of the pyridyl ring is twisted out of the square coordination plane about the metal {angle between planes in the range 25.6 (7) to 39.6 o (6)} for all four complexes. This reflects a degree of flexibility associated with the P-N chelate ring, something further exemplified by the variation of the ligand bite angle with values ranging from 82.71 (4) (3) to 85.29(8)° (7).…”

“…Subsequent heating of the solution at reflux for a further 18 h led to the formation of Ôpalladium blackÕ and a green solution, which showed no signal by 31 P { 1 H} NMR spectroscopy. Although not revealing the identity of the active catalytic species, these observations confirm both the partial resilience of unbound 1 and its complexes in MeOH, despite the presence of a potentially reactive polar P-N linkage, in line with previous observations regarding the stability of metal-bound aminophosphines [7,8].…”

“…For a number of years we have been interested in the preparation of chelating phosphorus-nitrogen scaffolds 0022 and have focussed our attention upon systems that could be prepared through the formation of a P-N bond [6,7]. This methodology is attractive not only because such reactions are generally easily achieved, but also because the resulting aminophosphine component is an electronically and sterically flexible donor moiety in its own right [8][9][10].…”

New Bulky Phosphino−Pyridine Ligands. Palladium and Nickel Complexes for the Catalytic Polymerization and Oligomerization of Ethylene

“…Due to the different properties of the phosphorus and nitrogen donors, the study of phosphine-imine ( P ∼ N ) ligands in coordination chemistry and catalysis has received much attention. − Recently, we demonstrated that palladium complexes 1 (Chart ) can stabilize various insertion intermediates such as CO and olefins/alkynes . However, complex 1 can only catalyze the di- and trimerization of ethylene .…”

Changes in ligand coordination mode induce bimetallic C–C coupling pathways

“…The similar 1 H chemical shifts and coupling values are consistent with other PdMe 2 complexes bearing asymmetric bidentate ligands. 51–53 The 1 H NMR signals correlate by 1 H– 13 C HSQC to doublets at δ C = −11.6 and 7.9, respectively, with coupling constants of 2 J CP = 6.04 and 117.8 Hz. These coupling constants are consistent with, respectively, cis - and trans -disposed methyls relative to the phosphine donor.…”