104324-84-7Relevant academic research and scientific papers
Synthesis and reaction chemistry of iridium(III) hydrides formed by the intramolecular N-H addition of hybrid phosphine amines to iridium(I)
Park, Soonheum,Johnson, M. Pontier,Roundhill, D. Max
, p. 1700 - 1707 (2008/10/08)
Monovalent P-bonded iridium and rhodium complexes MCl(1,5-COD)(o-Ph2PC6H4NHR) (R = CH2Ph, Et) have been prepared from [M(μ-Cl)(1,5-COD)]2 and o-Ph2PC6H4NHR. New P,N-chelate complexes [Ir(1,5-COD)(o-Ph2PC6H4NHR)]ClO4 are formed upon reaction of the iridium complexes with AgClO4. The amine arm of the chelate can be substituted by added ligands L to give [Ir(1,5-COD)(o-Ph2PC6H4NHR)L]ClO4 (L = pyridine, acetonitrile). Solution thermolysis of [Ir(1,5-COD)(o-Ph2PC6H4NHCH 2Ph)]ClO4 results in cyclometalation of the benzyl ring. The complex IrHCl(o-Ph2PC6H4NR)(o-Ph2PC 6H4NHR) (R = CH2Ph, Et) has been obtained from the reaction between [Ir(μ-Cl)(C8H12)2]2 and o-Ph2PC6H4NHR. The pathway involves N-H addition to iridium(I). Reversible protonation of IrHCl(o-Ph2PC6H4NR)(o-Ph2PC 6H4NHR) with HX gives [IrHCl(o-Ph2PC6H4NHR)2]X. The chloride ligand is replaced by CO to give two isomers of [IrH(o-Ph2PC6H4NR)CO(o-Ph2PC 6H4NHR)]Cl. The reaction between [Rh(μ-Cl)(C8H14)]2 and o-Ph2PC6H4NHCH2Ph gives the unstable complex [Rh(o-Ph2PC6H4NHCH2Ph) 2]Cl, which reacts with CO to give trans-RhCl(CO)(o-Ph2PC6H4NHCH 2Ph)2. Crystal data for [IrHCl(o-Ph2PC6H4NHCH2Ph) 2]Cl·2CDCl3: P21/n, a = 10.111 (4) A?, b = 25.886 (3) A?, c = 19.939 (3) A?, β = 93.03 (2)°, Z = 4, refined to R = 0.036, Rw = 0.054.
Iridium hydride complexes formed by the intramolecular N-H addition of hybrid phosphine amines to iridium(I)
Park, Soonheum,Hedden, David,Roundhill, D. Max
, p. 2151 - 2152 (2008/10/08)
The complexes [MCl(1,5-COD)]2 react with o-Ph2PC6H4NHR to give tetracoordinated complexes MCl(1,5-COD)(o-Ph2PC6H4NHR) (M = Rh, Ir, R = CH2Ph; M = Rh, R = Et) where the amine moiety is uncoordinated. Treating IrCl(1,5-COD)(o-Ph2PC6H4NHR) with AgClO4 gives the bis-chelate complexes [Ir(1,5-COD)(o-Ph2PC6H4NHR)]ClO4 (R = CH2Ph, Et). Thermolysis of [Ir(1,5-COD)(o-Ph2PC6H4NHCH 2Ph)]ClO4 causes C-cyclometalation to give [IrH(1,5-COD)(o-Ph2PC6H4NHCH2C 6H4)]ClO4. Treating [Ir(1,5-COD)(o-Ph2PC6H4NHEt)]ClO4 with L (L = py, MeCN) gives [IrL-(1,5-COD)(o-Ph2PC6H4NHEt)]ClO4, where the amine is uncoordinated. Cyclooctene in [IrCl(C8H14)2]2 is displaced by o-Ph2PC6H4NHR to give IrHCl(o-Ph2PC6H4NR)(o-Ph2PC 6H4NHR) (R = CH2Ph, Et). The deuterated analogue o-Ph2PC6H4NDR gives the iridium deuteride complex IrDCl(o-Ph2PC6H4NR)(o-Ph2PC 6H4NDR).
