Two families of variously-substituted N-pyrrolylphosphino-N'-arylaldimine ligands, 2-(aryl-N=CH)C4H3N-PR2 {R=Ph; R=Pri2N}, have been prepared from the corresponding pyrrolylaldimines . The donor characteristics/basicity of P-N-chelating and have been assessed using a combination of 31P{1H} NMR and IR spectroscopies through study of the magnitudes of 1JSeP for the phosphorus(V) selenides and , and measurement of nu(CO) for the complexes [RhCl(CO)(-kappa2-P,N)], respectively. The synthesis of the palladium(II) complexes [PdCl2(-kappa2-P,N)] was readily achieved from reaction of or with [PdCl2(MeCN)2] in CH2Cl2. X-Ray crystallographic studies of and confirm the chelating nature of the P-N ligands, which adopt a distorted 'envelope' conformation, and highlight the potentially significant steric demands of these metal scaffolds. Reaction of equimolar quantities of with [NiBr2(DME)] in MeCN afforded [NiBr2(-kappa2-P,N)], while the same reaction undertaken in CH2Cl2 with gave rise to the homoleptic bis(pyrrolatoimine) derivative [Ni{2-(mes-N=CH)C4H3N}2] in 45% yield, following P-N bond cleavage. Complex was characterised in the solid-state by X-ray crystallography. No identifiable metal-containing complexes could be obtained on reaction of with a variety of sources of Ni(II). The palladium dichloride complexes and proved inactive in combination with MAO or EtAlCl2 for ethylene polymerisation, and with methanesulfonic acid for CO/ethylene co-polymerisation. Contrastingly, the nickel complexes in combination with 4.5 eq. EtAlCl2 catalysed the formation of butenes and hexenes with moderate activity from ethylene at 1 bar.
Two families of variously-substituted N-pyrrolylphosphino-N'-arylaldimine liganpan>ds, pan> class="Chemical">2-(aryl-N=CH)C4H3N-PR2 {R=Ph; R=Pri2N}, have been prepared from the corresponding pyrrolylaldimines . The donor characteristics/basicity of P-N-chelating and have been assessed using a combination of 31P{1H} NMR and IR spectroscopies through study of the magnitudes of 1JSeP for the phosphorus(V) selenides and , and measurement of nu(CO) for the complexes [RhCl(CO)(-kappa2-P,N)], respectively. The synthesis of the palladium(II)complexes [PdCl2(-kappa2-P,N)] was readily achieved from reaction of or with [PdCl2(MeCN)2] in CH2Cl2. X-Ray crystallographic studies of and confirm the chelating nature of the P-N ligands, which adopt a distorted 'envelope' conformation, and highlight the potentially significant steric demands of these metal scaffolds. Reaction of equimolar quantities of with [NiBr2(DME)] in MeCN afforded [NiBr2(-kappa2-P,N)], while the same reaction undertaken in CH2Cl2 with gave rise to the homoleptic bis(pyrrolatoimine) derivative [Ni{2-(mes-N=CH)C4H3N}2] in 45% yield, following P-N bond cleavage. Complex was characterised in the solid-state by X-ray crystallography. No identifiable metal-containing complexes could be obtained on reaction of with a variety of sources of Ni(II). The palladium dichloridecomplexes and proved inactive in combination with MAO or EtAlCl2 for ethylene polymerisation, and with methanesulfonic acid for CO/ethyleneco-polymerisation. Contrastingly, the nickelcomplexes in combination with 4.5 eq. EtAlCl2 catalysed the formation of butenes and hexenes with moderate activity from ethylene at 1 bar.