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Title:Multinuclear NMR studies on solution structures and dynamics of triosmium hydrido carbonyl phosphine cluster compounds
Author(s):Koike, Makoto
Doctoral Committee Chair(s):Shapley, John R.
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Inorganic
Abstract:The reaction of ($\mu$-H)$\sb2$Os$\sb3$(CO)$\sb9$(PPh$\sb3$) with acetylene at room temperature provides two isomers of a hydridovinyl cluster. The solid-state structure of each isomer has been determined by single-crystal X-ray crystallography. The solution structures and dynamics have been studied by extensive $\sp{13}$C NMR studies, including $\sp{13}$C$\{\sp1$H$\}$ COSY and $\sp{13}$C spin saturation transfer experiments.
$\sp1$H and $\sp{13}$C NMR studies show that the reaction of ($\mu$-H)$\sb2$Os$\sb3$(CO)$\sb9$(PPh$\sb3$) with ethylene gives ($\mu$-H)$\sb2$Os$\sb3$(CO)$\sb9$(PPh$\sb3$)($\mu$-CHCH$\sb3$), instead of the previously formulated complex ($\mu$-H)(H)Os$\sb3$(CO)$\sb9$(PPh$\sb3$)(C$\sb2$H$\sb4$).
The reaction of ($\mu$-H)$\sb2$Os$\sb3$(CO)$\sb9$(PMe$\sb2$Ph) with Bu$\sp{\rm t}$NC produces two pairs of two isomers of an isonitrile cluster, ($\mu$-H)(H)Os$\sb3$(CO)$\sb9$(PMe$\sb2$Ph)(Bu$\sp{\rm t}$NC). The origin, structure, and dynamic behavior of these isomers have been investigated by $\sp1$H, $\sp{13}$C, and $\sp{31}$P NMR studies.
The reaction of ($\mu$-$\rm H)\sb2Os\sb3(CO)\sb9(PPh\sb3$) with ethereal diazomethane in chloroform gives a novel compound, (($\mu$-H)$\sb2$Os$\sb3$(CO)$\sb8$(PPh$\sb3$)$\sb2$) $\sb2$($\mu$-cis-CHCH=CHCH$\sb2$CH), in which two triosmium carbonyl units are connected through a hydrocarbon fragment. This formulation is based on data obtained from mass spectrometry, elemental analysis, and extensive $\sp1$H, $\sp{13}$C, and $\sp{31}$P NMR studies.
A combination of $\sp{13}$C$\{\sp1$H$\}$ COSY, selectively $\sp1$H decoupled $\sp{13}$C NMR, and $\sp{13}$C spin saturation transfer experiments on the pair of tautomers, ($\mu$-H)Os$\sb3$(*CO)$\sb{10}$($\mu$-CH$\sb3$)/($\mu$-H)$\sb2$Os$\sb3$(*CO)$\sb{10}$($\mu$-CH$\sb2$) has established the overall solution dynamics of these compounds.
Issue Date:1991
Type:Text
Language:English
URI:http://hdl.handle.net/2142/22734
Rights Information:Copyright 1991 Koike, Makoto
Date Available in IDEALS:2011-05-07
Identifier in Online Catalog:AAI9210874
OCLC Identifier:(UMI)AAI9210874


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