Synthesis and reactivity studies of high-nuclearity carbido carbonyl clusters of heptarhenium-iridium and decaruthenium

The cluster anion ($\rm Re\sb7C(CO)\sb{21}Ir(C\sb8H\sb{14})(CO)\rbrack \sp{2-}$ has been synthesized by the capping of ($\rm Re\sb7C(CO)\sb{21}\rbrack \sp{3-}$ with the in-situ generated cationic species from the reaction of ($\rm Ir(C\sb8H\sb{14})\sb2(CO)Cl\rbrack \sb2$ and AgBF$\sb4.$ This new heptarhenium-iridium compound reacts with two electron donors to give ligand-substituted compounds ($\rm Re\sb7C(CO)\sb{21}Ir(L)(CO)\rbrack \sp{2-}$ (L = CO, $\rm C\sb2H\sb4,$ PMePh$\sb2,$ and PPh$\sb3),$ and with triphenylsilane and allyl bromide to form the oxidative addition products ($\rm Re\sb7C(CO)\sb{21}Ir(H)(CO)(SiPh\sb3)\rbrack \sp{2-}$ and ($\rm Re\sb7C(CO)\sb{21}Ir(\eta\sp3C\sb3H\sb5)(CO)\rbrack \sp-.$ The reactivities at iridium parallel those of the indenyl complex $\rm (\eta\sp5C\sb9H\sb7)Ir(C\sb8H\sb{14})(CO),$ thus giving further support for the previously proposed analogy between ($\rm Re\sb7C(CO)\sb{21}\rbrack \sp{3-}$ and the cyclopentadienyl ligand and its derivatives. Formulation and characterization of these new compounds are based on elemental analysis, IR, $\sp1$H and $\sp{13}$C NMR spectroscopies, fast-atom bombardment mass spectrometry, and X-ray crystallography.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2011

Author dc:creator

• Ma, Linqing

Contributors dc:contributor

• Shapley, John R.

• Chemistry, Inorganic

Statement dc:rights

• Copyright 1991 Ma, Linqing

Language dc:language

eng

Identifier

AAI9210905
(UMI)AAI9210905

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/22793