Stepwise metal-assisted conversion of /eta//sup 2/-CSe/sub 2/ to /eta//sup 1/-Se/sub 2/CPEt/sub 3/, /eta//sup 2/-Se/sub 2/CO, and /eta//sup 2/-Se/sub 2/. Crystal structures of the complexes ((triphos)Rh(Se/sub 2/CO))BPh/sub 4/ x 0. 5CH/sub 2/Cl/sub 2/ x 0. 5C/sub 4/H/sub 9/OH and ((triphos)Rh(. mu. -Se/sub 2/)/sub 2/Rh(triphos)) (BPh/sub 4/)/sub 2/ x 2DMF (triphos = MeC(CH/sub 2/PPh/sub 2/)/sub 3/)
The reaction of (triphos)RhCl(/eta//sup 2/-CSe/sub 2/) (1) in CH/sub 2/Cl/sub 2/ with PEt/sub 3/ gives the phosphoniodiselenoformate complex (triphos)RhCl(Se/sub 2/CPEt/sub 3/) (2). Compound 2 reacts at room temperature in CH/sub 2/Cl/sub 2/ solution with dioxygen to yield OPEt/sub 3/ and (triphos)RhCl(Se/sub 2/CO) (3). The chloride ligand can be removed from 3 in CH/sub 2/Cl/sub 2/ by NaBPh/sub 4/ in 1-butanol to give the 16-electron complex ((triphos)Rh(Se/sub 2/CO))BPh/sub 4/ x 0.5CH/sub 2/Cl/sub 2/ x 0.5C/sub 4/H/sub 9/OH (4), which photochemically or thermally undergoes the chelotropic elimination of CO to form the bis(..mu..-diselenium) complex ((triphos)Rh(..mu..-Se/sub 2/)/sub 2/Rh(triphos))(BPh/sub 4/)/sub 2/ x 2DMF (5b). The crystal structures of 4 and 5b have been determined by x-ray crystallography and the results are presented here. The structure consists of monomeric complex cations ((triphos)Rh(Se/sub 2/CO))/sup +/, BPh/sub 4//sup -/ anions, and some amount of CH/sub 2/Cl/sub 2/ and 1-butanol molecules of crystallization. The metal atom is five-coordinated by the three phosphorus atoms of triphos and by the two selenium atoms of the diselenocarbonate ligand in a distorted-square-pyramidal environment. The structure consists of binuclear ((triphos)Rh(..mu..-Se/sub 2/)/sub 2/Rh(triphos))/sup 2 +/ cations, BPh/sub 4//sup -/ anions, and DMF molecules of crystallization. The system consists of two (triphos)Rh(/eta//sup 2/-Se/sub 2/) fragments related by a crystallographic inversion center. Each rhodium atom is coordinated by the three phosphorus atoms of triphos, an /eta//sup 2/-diselenium molecule, and one selenium atom from the other (triphos)Rh(/eta//sup 2/-Se/sub 2/) moiety. 27 references, 3 figures, 5 tables.
- Research Organization:
- Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione CNR, Firenze (Italy)
- OSTI ID:
- 6299002
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:21; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALKENES
AROMATICS
BORON COMPOUNDS
CARBONYLS
COMPLEXES
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
RHODIUM COMPLEXES
SELENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES