Multinuclear NMR studies on solution structures and dynamics of triosmium hydrido carbonyl phosphine cluster compounds

Koike, Makoto

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https://hdl.handle.net/2142/22734 Copy

Description

Title

Multinuclear NMR studies on solution structures and dynamics of triosmium hydrido carbonyl phosphine cluster compounds

Author(s)

Koike, Makoto

Issue Date

1991

Doctoral Committee Chair(s)

Shapley, John R.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

Chemistry, Inorganic

Language

eng

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.

Type of Resource

text

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http://hdl.handle.net/2142/22734

Copyright and License Information

Copyright 1991 Koike, Makoto

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