Rhodium(I) and rhodium(III) phosphine complexes with nonbridging benzenethiolato ligands: Preparation, structures, and chemical properties

Journal Article · Wed May 26 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00063a027· OSTI ID:5786096

Osakada, Kohtaro; Hataya, Kouji; Yamamoto, Takakazu ^[1]

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1. Tokyo Institute of Technology, Yokohama (Japan)

Reactions of NaSPh with [Rh(PMe[sub 3])[sub 4]]Cl and with RhCl(PMe[sub 3])[sub 3] give Rh(SPh)PMe[sub 3])[sub 3] (1), whose X-ray crystallography shows a square-planar coordination. Temperature-dependent NMR ([sup 1]H and [sup 31]P([sup 1]H)) spectra of 1 show fluxionality of the molecule due to intramolecular exchange of the ligands in the solution. Complex 1 reacts smoothly with air to give the dioxygen-coordinated complex Rh(SPh)(O[sub 2])(PMe[sub 3]0[sub 3] (2). X-ray crystallography shows a distorted trigonal bipyramidal coordination around the metal center having a dioxygen ligand with the O-O bond distance of 1.456(6) [angstrom]. Addition of air to the reaction mixture of [Rh(PMe[sub 3])[sub 4]]Cl with NaSC[sub 6]H[sub 4]-p-OMe gives the analogous dioxygen-coordinated complex Rh(SC[sub 6]H[sub 4]-p-OMe)(O[sub 2](PMe[sub 3])[sub 3] (3). Reaction of complex 1 with HSPh in hexane causes oxidative addition of the S-H bond to the metal center to give the Rh(III) complex cis,mer-RhH(SPh)[sub 2](PMe[sub 3])[sub 3] (4a) as the initial product. Further stirring of the reaction mixture at room temperature causes isomerization of 4a into trans,mer-RhH(SPh)[sub 2](PMe[sub 3])[sub 3] (4b). NMR ([sup 1]H and [sup 31]P) spectra of the complexes 4a and 4b as well as X-ray crystallography of 4b indicate their respective structures unambiguously. Reaction of DSPh (65% D) with 4a gives trans,mer-RhD9SPh)[sub 2](PMe[sub 3])[sub 3] (4b-d[sub 1]) in 55% isotopic purity, while similar reaction with 4b causes deuteration in 18%. Reaction of phenyl acetylene with complex 1 gives mer-RhH-(C[equivalent to]CPh)(SPh)(PMe[sub 3])[sub 3] (5) with the acetylide and the thiolato ligands at mutually trans positions.

• OSTI ID: 5786096
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:11; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHODIUM COMPLEXES
CHEMICAL REACTIONS
MOLECULAR STRUCTURE
CHEMICAL PREPARATION
DEUTERATION
HYDRIDES
ISOMERIZATION
NUCLEAR MAGNETIC RESONANCE
PHOSPHINES
PHOSPHORUS 31
TEMPERATURE DEPENDENCE
TEMPERATURE RANGE 0065-0273 K
TEMPERATURE RANGE 0273-0400 K
THIOLS
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
HYDROGEN COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
RESONANCE
SCATTERING
STABLE ISOTOPES
SYNTHESIS
TEMPERATURE RANGE
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties