Issue 5, 1988

Hydrido platinum metal macrocyclic complexes: the synthesis and single-crystal X-ray structure of cis-[IrCl(H)L1]PF6{L1=7-methyl-3,7,11,17-tetrazabicyclo[11.3.1]heptadeca-1(17),13,15-triene}

Abstract

Reaction of IrCl3·3H2O with one equivalent of 7-methyl-3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17),13,15-triene (L1) in refluxing aqueous EtOH for 72 h affords the hydridoiridium(III) complex [IrCl(H)L1]PF6. This crystallises in the monoclinic space group P21/c, with a= 10.028(4), b= 11.926(6), c= 16.539(9)Å, β= 99.23(4)°, and Z= 4. A single-crystal X-ray structure shows octahedral IrIII bound to the folded pyridine-2,6-diyl macrocycle L1[Ir–N(3) 2.080(11), Ir–N(11) 2.083(11), and Ir–N(17) 1.952(10)Å] with the fourth N donor, N(7), bent away to bind at an axial position [Ir–N(7) 2.266(11)Å]. The Ir atom lies 0.09 Å out of the triaza plane defined by N(3), N(11), and N(17). Chloro and hydrido ligands complete the octahedral co-ordination around the metal centre. The former [Ir–Cl 2.393(4)Å] lies trans to the pyridyl N(17) donor, with the latter trans to N(7);N(17)IrCl 175.7(3), HlrN(7) 172(5)°. The mechanism of formation of the complex, and the role of hydrido species as intermediates in the insertion of platinum metal ions into macrocyclic ligands, are discussed.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1988, 1165-1168

Hydrido platinum metal macrocyclic complexes: the synthesis and single-crystal X-ray structure of cis-[IrCl(H)L1]PF6{L1=7-methyl-3,7,11,17-tetrazabicyclo[11.3.1]heptadeca-1(17),13,15-triene}

A. J. Blake, T. I. Hyde and M. Schröder, J. Chem. Soc., Dalton Trans., 1988, 1165 DOI: 10.1039/DT9880001165

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