Syntheses, molecular structures, electrochemical and spectroscopic studies of dirhodium complexes containing axial Rh-C bond
The previously known Rh(II)Rh(III) complex (ap)[sub 4]Rh[sub 2]Cl (ap = 2-anilinopyridinate) was prepared by modified literature methods and used as synthetic intermediate. Three new Rh(II)Rh(III) dimers, (ap)[sub 4]Rh[sub 2]C[triple bond]CH, (ap)[sub 4]Rh[sub 2]CH=CH[sub 2] and (ap)[sub 4]Rh[sub 2]Ch[sub 3] were synthesized through nucleophilic substitution reaction of (ap)[sub 4]Rh[sub 2]Cl with a large excess of NaC[triple bond]CH, MgBrCH=CH[sub 2] or LiCH[sub 3], respectively. Two bis-dimers, (ap)[sub 4]Rh[sub 2] C[triple bond]CC[triple bond]CRh[sub 2] (ap)[sub 4] and (dpf)[sub 4] Rh[sub 2] CNC[sub 6] H[sub 4] NCRh[sub 2] (dpf)[sub 4], (dpf = N,N'-diphenylformamidinate) were also prepared by the reactions of (ap)[sub 4]Rh[sub 2]Cl and (CH[sub 3])[sub 3] SiC[triple bond]CC[triple bond]CSi(CH[sub 3])[sub 3] stepwise with BuLi as mediator, or the reaction of (dpf)[sub 4]Rh[sub 2] with CnC[sub 6]H[sub 4]NC at room temperature. All of these novel complexes were characterized by mass spectrometry, single crystal X-ray diffraction, electron spin resonance spectroscopy, UV-vis spectroscopy and electrochemical methods. The complexes which have C[triple bond]C or C[triple bond]NR functional groups were characterized by infrared spectroscopy or resonance Raman spectroscopy.
- Research Organization:
- Houston Univ., TX (United States)
- OSTI ID:
- 7166268
- Resource Relation:
- Other Information: Thesis (Ph.D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
PYRIDINES
CHEMICAL PREPARATION
STRUCTURAL CHEMICAL ANALYSIS
RHODIUM COMPLEXES
ANILINE
ELECTROCHEMISTRY
ELECTRONIC STRUCTURE
MOLECULAR STRUCTURE
ORGANOMETALLIC COMPOUNDS
AMINES
AROMATICS
AZINES
CHEMISTRY
COMPLEXES
HETEROCYCLIC COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties