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Shapley, John R. Koike, Makoto 2011-05-07T13:49:42Z 2011-05-07T13:49:42Z 1991 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. Made available in DSpace on 2011-05-07T13:49:42Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210874.pdf: 5846032 bytes, checksum: cba627e4d2785e45f7fcb9c41677bbf0 (MD5) Previous issue date: 1991 Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:59:38Z Item is restricted indefinitely. Restriction data tranferred 2014-07-01T11:28:09-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission Author emailed IDEALS and requested open access. Restrictions lifted by kappleg@illinois.edu 2015-6-16. Open AAI9210874 (UMI)AAI9210874 http://hdl.handle.net/2142/22734 eng Copyright 1991 Koike, Makoto Chemistry, Inorganic Multinuclear NMR studies on solution structures and dynamics of triosmium hydrido carbonyl phosphine cluster compounds text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.