2006
DOI: 10.1021/om051103z
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Ethylene Polymerization Using Discrete Nickel(II) Iminophosphonamide Complexes

Abstract: The syntheses and structures of the discrete (π-allyl)nickel iminophosphonamide (PN 2 ) complexes 2a-d from the reaction of (π-allyl)nickel bromide and the corresponding PN 2 ligands 3a,b or from the reaction of (π-allyl) 2 Ni and phosphorane 1 are reported. Complexes 2a,b are characterized by having long Ni-N distances coupled with an acute bite angle for the PN 2 ligand. The π-allyl ligands in complexes 2a-d are not fluxional on the NMR time scale at room temperature, although chemical exchange between the i… Show more

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Cited by 50 publications
(35 citation statements)
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“…Among transition metal complexes with κ 2 -N,N-heteroallylic ligands, the iminophosphonamides bearing a coordinated R 2 P(NR′) 2 − anion (NPN) are studied fragmentarily; there have been less than a hundred of molecular structures of NPN complexes established to date, that is in sharp contrast to more than a thousand of transition metal amidinate structures, according to the Cambridge Structural Database (CSD). The IV group metals, [1][2][3][4][5][6] chromium, 7-10 nickel [11][12][13][14][15] and copper [16][17][18][19][20][21][22] iminophosphonamides are the most studied, which is due to their catalytic application in cyclopropanation, 16,21,23 olefin oligomerization [7][8][9] and polymerization. 2,6,12,15,24,25 A few platinum metal group iminophosphonamides have been reported for palladium 24 and ruthenium 26 before 2009, when we started systematic studies of these complexes.…”
Section: Introductionmentioning
confidence: 99%
“…Among transition metal complexes with κ 2 -N,N-heteroallylic ligands, the iminophosphonamides bearing a coordinated R 2 P(NR′) 2 − anion (NPN) are studied fragmentarily; there have been less than a hundred of molecular structures of NPN complexes established to date, that is in sharp contrast to more than a thousand of transition metal amidinate structures, according to the Cambridge Structural Database (CSD). The IV group metals, [1][2][3][4][5][6] chromium, 7-10 nickel [11][12][13][14][15] and copper [16][17][18][19][20][21][22] iminophosphonamides are the most studied, which is due to their catalytic application in cyclopropanation, 16,21,23 olefin oligomerization [7][8][9] and polymerization. 2,6,12,15,24,25 A few platinum metal group iminophosphonamides have been reported for palladium 24 and ruthenium 26 before 2009, when we started systematic studies of these complexes.…”
Section: Introductionmentioning
confidence: 99%
“…The monoanionic charge is delocalized over the NPN backbone, [P(1)-N(1) 1.610 (2) . 37 This interaction is probably responsible for magnetic non-equivalence of o-Me groups that interact with Ni to that of those not involved in this interaction (vide supra).…”
Section: General Synthetic Methods For Lithium Derivatives (3 and 4)mentioning
confidence: 99%
“…34 No complex of Cu(II) with iminophosphonamides has been reported and only Cu(I) iminophosphonamide derivatives with a series of olefins as co-ligands have been reported. 35,36 The discrete (π-allyl)nickel(II) iminophosphonamides Ph 2 P(NR) 2 Ni(η 3 -C 3 H 5 ) (R = SiMe 3 or p-Me-C 6 H 4 ), 37 [Ni{Ph 2 P(NPh) 2 } 2 ] 38 and {Ph 2 P(NSiMe 3 ) 2 } NiPh(PPh 3 ) 37 are among the structurally characterized heteroleptic iminophosphonamides of Ni(II). The structurally characterized homoleptic iminophosphonamides of Ni(II) are Ni{iPr 2 P(NMe) 2 } 2 ]a n d [Ni{Ph 2 P(NSiMe 3 ) 2 } 2 ].…”
Section: Introductionmentioning
confidence: 99%
“…Such polymerization takes place only the ligand contains SiMe 3 substituents at the coordinating nitrogen. Recently, Ni complexes with iminophosphonamide ligands (9f) were synthesized [162,163]. Although the isolated complexes are inactive for ethylene polymerization, the catalysts prepared in situ by mixing the ligands and Ni(cod) 2 or Ni(allyl) 2 afforded branched polyethylene.…”
Section: Neutral Complexes With Other Monoanionic Ligandsmentioning
confidence: 99%