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研究生:黃敏英
研究生(外文):Huang, Min-Ying
論文名稱:以NMR遲緩的方法對金屬羰基錯合物回饋電子的定量研究及CCl3CN再定位運動的測定
論文名稱(外文):Quantitative Studies of p-Back Bonding Electrons in Metal Carbonyl Complexes and Investigation of Reorientational Dynamics of CCl3CN by NMR Relaxation Techniques
指導教授:王小萍
指導教授(外文):Wang, Xiao-Ping
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:1998
畢業學年度:86
語文別:中文
論文頁數:70
中文關鍵詞:核遲共振金屬羰基錯合物回饋電子再定位運動化學工程化學
外文關鍵詞:NMRp-back bondingMetal Carbonyl ComolexesReorientationalCCl3CNCHEMICAL-ENGINEERINGCHEMISTRY
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NMR spectroscopic technique can
be applied on structure elucida
tion,probeof molecular motion an
d determinationof phsical proper
ties.The first subjectof this re
search is to evaluate electron d
ensity dispersed onto the carbon
yl’s antibonding pi-orbitalsin t
ungsten pentacarbonyl complexes,
W(CO)5L{L=PPh3,PPh2Me,PPhMe2,PMe
3}.Experimental results indicate
that these phosphines are subst
antiallyp-accepting ligands.The
p-electrondensity on the rest ca
rbonyl groups are affected by su
bstituents’ s-basicityand p-acid
ity in a competitive manner.Toge
ther with earlier studies,it is
found that substitution effects
on 2p-population for axial and r
adial carbonyls are well predict
ed by number of metal’s d-orbita
ls through which back-bonding pr
oceeds.For p-neutral or p-donati
ng ligands,,these effects are st
rongly directional.The second pa
rt of this research is to invest
igate reorientational dynamics i
nCCl3CN,which is characterized b
y thespinning and tumbling diffu
sion constant.These two motions
can be solved by measuring the r
eorientationalcorrelation times,
tc,for both the CN and CCl vecto
rs. Measurements of the values o
f tc were accomplished bynitroge
n-14 and chlorine-35 NMR quadrup
olar relaxation time(T2q)experim
ents.We have also utilized carbo
n-13 chemical shift anisotropysp
in-lattice relaxation times(T1CS
A) todetermine tc(CN).Derived ma
gnitudes ofspinning and tumbling
diffusion constants reveal this
molecule undergoes a significan
tly anisotropicreorientation.Reo
rientational diffusionconstants
obtained from T1CSA(13C) andT2q(
14N)are in good consistence at v
arious temperatures. Hence,this
studyhas laid foundation for fut
ure researchperformed on investi
gation of bonding in M-CN comple
xes.

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