Carboxylato compounds of chromium, copper, rhodium and molybdenum and new advances in the chemistry of V2(NXN)4

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Title: Carboxylato compounds of chromium, copper, rhodium and molybdenum and new advances in the chemistry of V2(NXN)4
Author: Hillard, Elizabeth Anne
Abstract: This dissertation comprises the investigation of two subjects in the field of dimetal paddlewheel -type compounds containing metal -metal bonds : unsolvated transition metal carboxylates and triply bonded divanadium compounds . The first subject is very mature ; dichromium tetraacetate was first synthesized in 1844 , and hundreds of dimetal tetracarboxylates have been structurally characterized to date . A general question concerning the complexes of the type M2L4 -Xn (where n = 0 to 2 ) is the extent to which the M -M distances are influenced by the presence of axial ligands , X . However , virtually none of the carboxylato complexes crystallize without axial ligands . In the solid state , in the absence of a coordinating solvent , the dimetal units often act as axial ligands to one another . In order to exclude axial coordination , both from donor solvent molecules , and from the aggregation of M24+ units , we have successfully used the bulky 2 ,4 ,6 -triisopropylbenzoate ligand to bridge the dimetal core . We have investigated the triisopropylbenzoato complexes of some metals which are known for their ability to form a vast array of tetracarboxylato complexes , namely chromium , copper , molybdenum , and rhodium , and have found that these novel compounds display some interesting structural and chemical properties . The second subject of this dissertation is much more contemporary . Although compounds containing multiple bonds between metal atoms have been known since 1964 , the first triply -bonded divanadium compound was not synthesized until 1992 , and only two additional compounds of this type have been made in the intervening ten years . In order to extend this chemistry , several additional compounds containing a triply bonded V24+ core have recently been characterized . In our study of these compounds , we have discovered the first example of a stable paddlewheel -type compound with a M23+ core .
URI: http : / /hdl .handle .net /1969 .1 /57
Date: 2004-09-30

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Carboxylato compounds of chromium, copper, rhodium and molybdenum and new advances in the chemistry of V2(NXN)4. Available electronically from http : / /hdl .handle .net /1969 .1 /57 .

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