Heterometallic Ag-I-Ir-Iii Hydride Coordination Polymers Bridged By Ir-Iii Metalloligands

A new type of Ir-III metalloligands containing an unsaturated nitrogen coordination site, [Ir(H)(2)(PPh3)(2)(pprd)]BF(4)2CHCl(3) (1), [Ir(H)(2)(PPh3)(2)(Me(2)bpm)]BF4CHCl3 (2), {[Ir(H)(2)(PPh3)(2)(Me(2)bpm)]PF6CHCl3}(4) (3), [Ir(H)(2)(PPh3)(2)(biqz)]BF(4)2CHCl(3) (4), and [Ir(H)(2)(PPh3)(2)(biqz)]PF6 (5), have been prepared by reaction of [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]X (X = BF4 or PF6) with 4-(2-pyridyl)pyrimidine (pprd), 6,6-dimethyl-4,4-bipyrimidine (Me(2)bpm), or 4,4-biquinazoline (biqz). Subsequently, three novel heterometallic Ag-I-Ir-III hydride coordination polymers, {[Ir(H)(2)(-pprd)(PPh3)(2)Ag(-CF3COO)]BF4Me2CO}(n) (6), {[Ir(H)(2)(-biqz)(PPh3)(2)Ag-2(-CF3COO)(3)]Me2CO}(n) (7), and {[Ir(H)(2)(-Me(2)bpm)(PPh3)(2)Ag-2(-CF3COO)(2)]PF(6)2Me(2)CO}(n) (8) have been constructed by reaction of the Ir-III metalloligands 1, 3, and 5 with AgCF3COO. In coordination polymer 6, the [Ir(H)(2)(PPh3)(2)(pprd)](3+) units are linked through the Ag-I atoms to form a 1D zigzag chain structure. In coordination polymer 7, the dinuclear [Ag-2(-CF3COO)(3)](-) units are linked through the terminal N atoms of biqz in two different [Ir(H)(2)(PPh3)(2)(biqz)](3+) units to form a 1D zigzag chain structure. In coordination polymer 8, the [Ag-2(-CF3COO)(2)] frameworks are linked through the terminal N atoms of Me(2)bpm and the Ir-III atom in two different [Ir(H)(2)(PPh3)(2)(Me(2)bpm)](3+) units to form a waved rectangular cavity. These waved rectangular cavities are connected to each other to afford a unique 2D sheet structure.