Synthetic and Structural Investigations on the Reactivity of the Cd–I Bond in [ICd{Zr2(OPri)9}] to Construct New Mixed-Metal Alkoxides

New mixed-metal alkoxides of general formula [XCd­{Zr2(OPri)9}]n (X = −C2F5, −C6F5, −C6F4-4-H, −NO3, −NCO, −SO3CF3, −O2CCF3, −O2CC2F5, −O2CCH3, −ClO4, −CN, −SO4; n = 1, 2) were obtained by the scission of the Cd–I bond in the iodo heterobimetallic isopropoxide [ICd­{Zr2(OPri)9}] (1), whereby the underlying synthetic strategies involve metathesis reactions with silver salts or Lewis acid–base interactions between the Brønsted acid [Zr­(OPri)4(HOPri)]2 and bis­(fluoroorgano)cadmium (Cd­(Rf)2) compounds. The new compounds were characterized by multinuclear NMR spectroscopy, elemental analysis, and mass spectrometry. The results of X-ray diffraction analysis of [(F5C6)­Cd­{Zr2(OPri)9}] (2), [(4-H-F4C6)­Cd­{Zr2(OPri)9}] (3), [(F5C2)­Cd­{Zr2(OPri)9}]2 (4), [(ONO2)­Cd­{Zr2(OPri)9}]2 (5), [(CH3CO2)­Cd­{Zr2(OPri)9}] (6), [(O2ClO2)­(H5C3N)­Cd­{Zr2(OPri)9}] (7), [(μ-O2ClO2)­Cd­{Zr2(OPri)9}]2 (8), [(μ-O2CCF3)­Cd­{Zr2(OPri)8(O2CCF3)}]2 (9), [(μ-O2CC2F5)­Cd­{Zr2(OPri)8(O2CC2F5)}]2 (10), [(μ­(O,N)-OCN)­Cd­{Zr2(OPri)9}]2 (11), and [(μ-O2SOCF3)­Cd­{Zr2(OPri)9}]2 (12) revealed the molecular framework to be formally constituted by tetradentate coordination of a nonaisopropoxo dizirconate unit, {Zr2(OPri)9}−, to a CdX+ unit. In solution and in the solid state, 1–7 exist as monomers, whereas compounds 8–12 form dimers.