1196695-29-0Relevant academic research and scientific papers
Synthesis, structures and reactivity of 2-phosphorylmethyl-1H-pyrrolato complexes of titanium, yttrium and zinc
Broomfield, Lewis M.,Wright, Joseph A.,Bochmann, Manfred
experimental part, p. 8269 - 8279 (2010/03/04)
The reaction of secondary phosphines HPR2 (R = Ph, Cy) with pyrrole-2-aldehydes gives a new family of 2-phosphorylmethyl-1H-pyrroles as potentially chelating mono-anionic ligands. The reaction with Ti(NMe 2)4 affords octahedral Ti(NMe2) 2{NC4H2(4-R′)CH2P(O)R 2}2 (R′ = H, But). While the diphenylphosphoryl complexes adopt a configuration with trans-pyrrolato ligands, the dicyclohexyl analogue prefers an all-cis conformation, with profound consequences on metal-ligand bonding. The reaction of sterically undemanding HNC4H3CH2P(O)Ph2 with Y[N(SiHMe 2)2]3(THF)2 give the homoleptic complex Y[NC4H3CH2P(O)Ph2] 3; mixed-ligand intermediates Y[N(SiHMe2) 2]2(N-O) and Y[N(SiHMe2)2](N-O) 2 were identifiable but could not be isolated. The bulky ligand HNC4H2(5-But)CH2P(O)Ph2 does not react with Ti(NMe2)4 but protolyses Zn[N(SiMe3)2]2 to give a 1: 2 complex Zn(N-O)2 as the only isolable product. On the other hand, its reaction with Y[N(SiHMe2)2]3(THF)2 affords the mono-amido complex Y{N(SiHMe2)2}{NC 4H3(5-But)CH2P(O)Ph 2}2 which shows good activity for the ring-opening polymerisation of cyclic esters. The Royal Society of Chemistry 2009.
Synthesis of neutral and zwitterionic phosphinomethylpyrrolato complexes of nickel
Broomfield, Lewis M.,Boschert, David,Wright, Joseph A.,Hughes, David L.,Bochmann, Manfred
supporting information; experimental part, p. 4084 - 4089 (2010/03/04)
Potassium salts of the new 2-phosphinomethyl-1H-pyrroles, K[R2PCH2C4H3N] (R = Ph, Cy) react with (η3-allyl)nickel bromide to give the chelate complexes (R2PCH2C4H3N)Ni(allyl), whereas the sterically hindered 2-diphenylphosphinomethyl-5-t-butyl-1H-pyrrole and (η3-allyl)nickel bromide afford a phosphine adduct (HNC4H2-5-But-2-CH2PPh2 )Ni(allyl)Br which is stabilized by an intramolecular NH?Br hydrogen bond. The addition of B(C6F5)3 to (R2PCH2C4H3N)Ni(allyl) leads to an electrophilic attack in 5-position of the pyrrole ring, to give the thermally unstable zwitterions (η3-C3H5)Ni[NC4H 3(2-CH2PR2)-5-B(C6F5) 3] which catalyse the isomerisation of 1-hexene. The addition of B(C6F5)3 is reversible, and slow ligand rearrangement to Ni(N-P)2 products appears to be the major catalyst deactivation pathway.
