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{Zr-2(OPri)(9)}] (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{Zr-2(OPri)(9)}] (1), whereby the underlying synthetic strategies involve metathesis reactions with silver salts or Lewis acid-base interactions between the Bronsted acid [Zr-(OPri)(4)(HOPri)](2) and bis(fluoroorgano)cadmium (Cd(R-f)(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{Zr-2(OPri)(9)}] (2), [(4-H-F4C6)Cd{Zr-2(OPri)(9)}] (3), [(F5C2)Cd{Zr-2(OPri)(9)}](2) (4), [(ONO2)Cd{Zr-2(OPri)(9)}](2) (5), [(CH3CO2)Cd(Zr-2(OPri)(9)}] (6), [(O2ClO2)(H5C3N)Cd{Zr-2(OPri)(9)}] (7), [(mu-O2ClO2)Cd{Zr-2(OPri)(9)}](2) (8), [(mu-O2CCF3)-Cd{Zr-2(OPri)(8)(O2CCF3)}](2) (9), [(mu-O2CC2F5)Cd{Zr-2(OPri)(8)(O2CC2F5)}](2) (10), [(mu(O,N)-OCN)Cd{Zr-2(OPri)(9)}](2) (11), and [(mu-O2SOCF3)Cd{Zr-2(OPri)(9)}](2) (12) revealed the molecular framework to be formally constituted by tetradentate coordination of a nonaisopropoxo dizirconate unit, {Zr-2(OPri)(9)}(-), to a CdX+ unit. In solution and in the solid state, 1-7 exist as monomers, whereas compounds 8-12 form dimers.