135107-52-7Relevant academic research and scientific papers
Assessing the effects of metal ion proximity on a trans-Ir(CO)Cl(phosphine)2 unit. Structural studies of potassium(I), tin(II), and lead(II) complexes of (crown-P2)Ir(CO)Cl
Balch, Alan L.,Neve, Francesco,Olmstead, Marilyn M.
, p. 3395 - 3402 (2008/10/08)
Addition of lead(II) or tin(III) salts to (crown-P2)Ir(CO)Cl (crown-P2 is Ph2PCH2N{CH2CH2OCH 2CH2OCH2CH2}2NCH 2PPh2) results in incorporation of the added main-group ion into the diaza crown ether portion. Yellow-orange crystals of [ClPb(crown-P2)Ir(CO)Cl]Cl·2CH2Cl2 crystallize in the orthorhombic space group Pc21b (No. 29) with a = 9.766 (4) A?, b = 22.291 (8) A?, and c = 23.159 (10) A? at 130 K with Z = 4. Refinement of 288 parameters and 3321 reflections yielded R = 0.070 and Rw = 0.074. The lead ion is coordinated to a terminal chloride and surrounded by the diaza-crown ligand so that it sits 3.117 (1) A? above the nearly planar trans-Ir(CO)ClP2 portion. Yellow-orange needles of [ClSn(crown-P2)Ir(CO)Cl]SnCl3·CHCl3 also form in the orthorhombic space group Pc21b (No. 29) with a = 9.719 (2) A?, b = 22.391 (5) A?, and c = 22.782 (7) A? at 130 K with Z = 4. Refinement of 2876 reflection and 300 parameters gave R = 0.0569 and Rw = 0.059. The cation is similar to the lead analogue with the Sn-Ir distance of 2.920 (2) A?. Potassium iodide reacts with (crown-P2)Ir(CO)Cl to form [K(crown-P2)Ir(CO)I]I, which crystallizes as a tris(dichloromethane) solvate in the orthorhombic space group Pbca with a = 21.936 (2) A?, b = 21.868 (12) A?, and c = 21.511 (8) A? at 130 K with Z = 8. Refinement of 303 parameters and 2761 reflections yielded R = 0.059 and Rw = 0.056. The potassium sits within the diaza-crown portion, 3.331 (6) A? away from the iridium. The lead/indium and tin/iridium complexes show distinctly new electronic absorption spectra indicative of Pb-Ir and Sn-Ir bonding. These complexes are photoluminescent at 77 K in frozen dichloromethane solution. In contrast, the potassium and sodium adducts of (crown-P2)Ir(CO)Cl show only minor perturbations of the characteristic absorption spectrum of the Ir(CO)ClP2 unit and do not show photoluminescence.
