Synthesis, x-ray, and low-temperature neutron diffraction study of a rhodium (V) complex: dihydridobis(triethylsilyl)-pentamethylcyclopentadienylrhodium
Reaction of (C/sub 5/ qentamethyl Rh)/sub 2/Cl/sub 4/) (1) with triethylsilane leads to the novel rhodium(V) complex (eta/sup 5/-C/sub 5/Me/sub 5/Rh(H)/sub 2/(SiE-triethyl/sub 3/)/sub 2/) (2) characterized by NMR spectra (/sup 1/H, /sup 13/C, /sup 29/Si, and /sup 103/Rh), X-ray diffraction, and neutron diffraction at 20 K. The complex shows a four-legged piano stool geometry with the pentamethylcyclopentadienyl eta/sub 5/-bonded to the rhodium (average Rh-C, 2.283 (9) A) on top and the two triethylsilyl ligands trans in the basal plane (Rh-Si, 2.379 (2) A). The neutron diffraction analysis located the two hydrides, which are trans to each other and cis to the triethylsilyls in the basal plane. The mean Rh-H distance is 1.581 (3) A, and the H-Rh-H angle is 94.8 (2)/sup 0/. Complex 2 is rather stable, but it reacts under forcing conditions with neutral ligands (triphenylphosphine, CO, or maleic anhydride) to give (C/sub 5/Me/sub 5/Rh(PPh/sub 3/)H(SiEt/sub 3/)), (C/sub 5/Me/sub 5/Rh(CO)/sub 2/), or (C/sub 5/M3/5Rh(maleic anhydride)/sup 2/). It reacts more easily with electrophiles such as HBF/sub 4/ to give (C/sub 5/Me/sub 5/Rh)/sub 4/H/sub 4/)/sup 2 +/, with HCl to give 1, with AgBF/sub 4/ in MeCN to give (C/sub 5/Me/sub 5/Rh(MeCN)/sub 3/)/sup 2 +/, and with I/sub 2/ to give ((C/sub 5/Me/sub 5/Rh)/sub 2/I/sub 4/). The predominant mode of reaction involves reductive elimination of Et/sub 3/Si-H, which can be strongly promoted by an electrophile. 43 references, 3 figures, 3 tables.
- Research Organization:
- The Univ., Sheffield, England
- OSTI ID:
- 6458569
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 106:19
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHODIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
BORON HYDRIDES
CARBON MONOXIDE
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
CYANIDES
CYCLOALKENES
DIENES
EXPERIMENTAL DATA
HYDROCHLORIC ACID
IODINE
LIGANDS
MOLECULAR STRUCTURE
NEUTRON DIFFRACTION
NMR SPECTRA
ORGANOMETALLIC COMPOUNDS
RHODIUM HYDRIDES
SILANES
SILVER FLUORIDES
STABILITY
VERY LOW TEMPERATURE
X-RAY DIFFRACTION
ALKENES
BORON COMPOUNDS
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
ELEMENTS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HALOGENS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POLYENES
REFRACTORY METAL COMPOUNDS
RHODIUM COMPOUNDS
SCATTERING
SILICON COMPOUNDS
SILVER COMPOUNDS
SPECTRA
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)